What are the raw materials for toy manufacturing?

The environmental protection innovation of plastic plasticizer industry, an important raw material for toy production, is imminent.

First of all, the plasticizer market in China is facing environmental pressure.

Plasticizer is one of the largest plastic additives in the world. In recent years, China has become the largest producer and consumer of plasticizers in Asia. With the improvement of environmental awareness all over the world, the plastic products such as medicine, food packaging, daily necessities and toys put forward higher purity and hygiene requirements for the main plasticizer DOP, but at present, the main plasticizer produced by domestic enterprises is difficult to meet the environmental requirements in many properties, especially hygiene and low toxicity. European Union and Russian successively imported plastic toys from China, and some plastic toys originating in China were found to contain toxic polyvinyl chloride plasticized diisononyl phthalate (DINP) and diethyl hexyl phthalate (DEHP, or DOP).

For a long time, o-benzene products have been the main plasticizer, but with the more and more extensive application of DOP in food and medicine industries, its toxicity has attracted more and more attention. It has been found that when people input blood stored in PVC plastic bags, DOP products will be found in the human body, especially in the lungs. 1982, the authoritative American National Cancer Institute made a biological identification of the carcinogenicity of DOP, and concluded that DOP is a carcinogen in rats and mice, which can cause liver cancer in rodents. As a result, the poison of DOP has attracted global attention. Although it is still controversial whether it will cause cancer, all countries have taken corresponding measures because of its potential carcinogenic suspicion. According to the research results of the National Cancer Institute, the US Environmental Protection Agency has stopped producing six new phthalates. DOP is only used for food packaging with high water content, and meat packaging must be replaced by other non-toxic plasticizer products. The Swiss government has decided to ban the use of DOP in children's toys. Germany has banned the use of DOP in all plastic products related to human health and food. Japan has banned the use of DOP in medical device-related products, which is limited to industrial plastic products.

According to the research results and standards issued by Europe, America, Japan and South Korea, DOP(DEHP) is more harmful than DOA(DEHA). EFSA of the European Food Safety Agency stipulates that the concentration of DEHA in human body above 0.3 mg/kg is considered unsafe, while the concentration of DEHP above 0.05 mg/kg is considered unsafe. DOA and DOP are plasticizers widely used in PVC food preservative films in China. In particular, DOP is the most used plasticizer, which is widely used in food packaging products. Among the ten main plasticizers allowed to be used in PVC cling film in China, the first one is dioctyl adipate (DEHA, abbreviated as DOA), and the last three are phthalate esters DBP, DOP and DIOP, all of which are quite toxic to DEHA. Due to the high production cost of DOA, most domestic PVC plastic wrap manufacturers use DOP and DBP as main plasticizers, so the plastic wrap produced in this way, especially for meat products with high fat content, or for packaging food in microwave ovens, will migrate to the packaged food, causing potential harm to human health. However, it is relatively safer to use on vegetables, especially those that need to be cleaned before eating or making food.

Although the international debate on whether DOP is carcinogenic is still going on, it is potentially carcinogenic, and international measures have been taken to limit the use of DOP. According to the research results of the National Cancer Institute, the US Environmental Protection Agency has stopped the industrial production of six phthalates. The Swiss government decided to ban the use of DOP in children's toys; Germany has banned the use of DOP in all plastic products related to human body and hygienic food: in Japan, DOP is only used as a plastic additive in plastic products in factories. At present, the world has accelerated the research and development of non-toxic plasticizer products, especially the basic application research of plastic products with high hygiene requirements. However, in China, there is still a big market for plasticizers that have been eliminated by foreign countries, such as DOP. Plasticizer manufacturers do not pay enough attention to the development and promotion of new non-toxic plasticizers. 80% of plasticizers in the domestic market are plasticizers such as DOP and DBP (dibutyl phthalate), and low price is the most critical factor. DOP is also listed as one of the plasticizers that can be used in food packaging in the national standard Hygienic Standard for Food Containers and Packaging Materials.

The latest test results of Tongji University show that when edible oil is bottled in plastic, plasticizer harmful to human body will be dissolved in edible oil. The research team led by Professor Li Shuguang from Tongji University School of Basic Medicine collected plastic barrels of soybean salad oil, blended oil and peanut oil with different brands and different factory dates in the market, as well as bulk soybean oil sold in the market, solid shortening of fried food in fast food restaurants and concentrated oil collected by kitchen range hoods of residents. After testing these samples, the research team found that almost all brands of plastic barrel edible oil contain "DBP" and "DOP", which are phthalate plasticizers commonly used in the plastic industry, while bulk soybean oil and solid shortening without plastic containers contain almost no plasticizer. It is inferred that the plasticizer detected in edible oil mainly comes from its plastic container. At present, the oil used by thousands of families in Qian Qian for three meals a day is mostly plastic barrels of edible oil purchased from the market. However, at present, plasticizers are not included in the physical and chemical indexes of edible oil inspection in national standards, and the content of plasticizers is not stipulated and required. Due to the lag of relevant standards in China, this is actually just the tip of the iceberg of plasticizer pollution. Plasticizers have a wide range of uses, a large pollution area and a large number of people, which is even worse than pesticides and DDT.

Second, environmental protection plasticizer new products

Enterprises should intensify research and development, develop new varieties of plasticizers, bypass technical barriers and reoccupy the international market. At present, the development of environmental protection plasticizer in the world obviously lags behind the needs of production and life. With the progress of science and technology, some traditional materials may be eliminated. It is a key link for the development of plastic products industry to develop new environmentally-friendly plasticizers with non-toxicity, low price and good addition effect as substitute materials.

1. citrate

Citrate product, as a new type of green plastic plasticizer, is non-toxic and tasteless, and can replace the traditional phthalate plasticizer. Widely used in food and medical device packaging, cosmetics, daily necessities, toys, military materials and other fields, but also an important chemical intermediate. Among them, acetyl citrate has excellent performance and wide application. It is not only a nontoxic and odorless green plastic plasticizer, but also can be used as a stabilizer of polyvinylidene chloride and an improver of adhesion between film and metal. Its glue still has strong adhesion after soaking in water for a long time.

Developed countries such as the United States and the European Union have successively promulgated laws and regulations to allow citrate products to be used as one of the plastic additives closely related to the human body, such as children's toys, sanitary products, medical devices, artificial leather, etc., and have higher hygiene requirements. China began to develop citrate in the mid-1990s. Jiangsu Raymond Chemical Technology Co., Ltd. grasps the market development trend and has long-term experience in the production and development of plasticizer products. The company has built a device with an annual output of 5,000 tons of citrate in China, and 40% of its products have entered the United States, Japan, Europe and other places.

Citrates produced in large quantities in China, such as tributyl citrate (TBC), trioctyl citrate (TOC), tributyl acetocitrate (ATBC) and trioctyl acetocitrate (ATOC), are considered as the safest plasticizers, which can be used in various PVC products, but they are easier to precipitate than DOP. At present, China has developed its own environmental protection plasticizer TBC, which has been applied to pharmaceutical products and can be gradually popularized in other production industries in the future.

2. 1.2 diisopropyl monocyclohexane dicarboxylic acid

1, 2- diisopropyl cyclohexanedicarboxylate is a colorless, transparent and slightly odorous anhydrous liquid with almost no fluidity. Soluble in many solvents, good compatibility with many common plasticizer monomers of PVC, and almost insoluble in water. It can be used for stomach tubes, infusion bags and other soft medical products, and can provide toy factories with an ideal solution that meets the safety requirements and the requirements of the new EU regulations.

3. Hysmans 168 plasticizer

Eastman NL 68, a new plasticizer from Eastman Company, was widely welcomed by the market as soon as it came out, because it did not contain harmful phthalate esters. This new plasticizer is non-toxic, does not contain estrogen and antiandrogen substances, does not cause carcinogens and does not cause peroxisome proliferation. Hysmans 168 plasticizer is the lowest risk choice, and it is also a simple plasticizer substitute for manufacturers who are looking for other plasticizers to produce children's toys that can be put in their mouths. This plasticizer meets the highest standards required by laws and regulations, and its non-toxic characteristics reassure many toy manufacturers and consumers. Plasticizer does not need to be reconfigured, which reduces the risk of expensive product recall and customer complaints caused by secondary configuration errors. Because of its low initial viscosity, excellent viscosity stability and processability, plasticizer can meet the requirements of high-speed molding production efficiency and cycle time, and can ensure consistent surface thickness.

4. Plasticizer for biodegradable plastics

A project partly funded by the British government has successfully developed a plasticizer for biodegradable plastics, which can be used in films and other flexible packaging of polylactic acid (PLA) and can greatly improve the mechanical properties of PLA. The project is supported by the British government's sustainable development technology start-up plan, which improves the flexibility of conventional hard PLA and its ductility can be increased from 5% to 320%. This kind of plasticizer is biodegradable, and its dosage in products is 10% ~ 20% of the dosage of additives. This modifier is based on the block copolymer generated between PLA and polyethylene glycol. The modified PLA can disappear from the mixture within 20 ~ 25 days. At present, this kind of additive has been produced on an industrial scale.

Third, promote the healthy development of plasticizers in China.

1. Solve the problem of lagging plasticizer standard.

At present, China's foreign trade export is facing a more severe external environment. What needs special attention is that there is an increasingly obvious trend for importing countries to restrict the export of China products and protect their own industries by raising quarantine standards and increasing testing items. At present, Europe, America, Japan, South Korea and other countries have used safe and environmentally friendly plasticizers such as citric acid ester and epoxy ester as substitute products, and have promulgated standards and regulations prohibiting the use of DOA and DOP in products that come into contact with human body, such as food packaging, medical supplies and children's toys. In China's national standards, DOA and DOP are clearly allowed. Although it is still inconclusive whether these plasticizer varieties cause cancer, due to the lag of relevant standards in China, the export of many domestic plastic products is blocked, and products containing expired plasticizers enter China on a large scale. The problem of lagging plasticizer standards in China needs to be solved urgently.

2. Promote risk assessment.

European Commission Plasticizer and Intermediate (ECP 1) Technology: ikePenman, chairman of the working group and senior toxicology consultant of ExxonMobil Petrochemical Company, said that the decisive factor to judge whether a plasticizer is available is the result of risk assessment, not the result of toxicity test. China Plasticizer Industry Association Chairman Chris also believes that following the trend without scientific basis will not be conducive to the healthy development of China's plasticizer and plastic industry, so it is necessary to strengthen the toxicity experiment and risk assessment of China's plasticizer.

The key to judge whether a plasticizer can be used is not the toxicity result of animal experiments, but the relationship between dose and toxicity, exposure and harmfulness, and the relationship between substance migration and migration speed and exposure, and then relevant risk control measures are formulated to minimize the harm to the public and the environment through scientific analysis and means. However, it is hasty and unscientific to take restrictive measures only based on the results of hazard identification. The international management of chemicals including plasticizers will become stricter and more scientific.

The registration, assessment, authorization and restriction system of chemicals in EU will be implemented before 2008, and risk assessment will be accepted by more and more people and become the basis for formulating various relevant laws. At present, the animal toxicity test and risk assessment of plasticizers in China are still very weak, which is very unfavorable to the healthy development of the industry. Relevant domestic parties should attach importance to risk assessment.

3. Promote the structural adjustment of plasticizer industry

Plasticizer plays an indispensable role in providing high-quality plastic products for human beings. However, its variety structure is constantly adjusting and changing, the development speed of new technology is accelerating, new varieties emerge one after another, the detection means are more advanced and the evaluation method is more reasonable. Plasticizers are constantly improved in such a cycle of "development and application-toxicology test-risk assessment-redevelopment". Therefore, the correct use of plasticizers is the key to the healthy development of this industry. To achieve this, plasticizer enterprises should work hard on structural adjustment. Foreign countries are vigorously promoting so-called non-toxic or environmentally friendly and biodegradable plasticizers. The so-called non-toxic and environmental protection are also relative. Such as DIHCN (diisononyl cyclohexanedicarboxylate), E-l68 plasticizer, EBN BET (polyol mixed ester of isooctanoic acid and benzoic acid) plasticizer, polyester plasticizer condensed with adipic acid and polyol, etc. At present, the production of environmentally friendly and nontoxic plasticizer in China faces two major problems: one is that there are many by-products and the yield is not high; The other is low output and high cost. Good products, such as citric acid ester, have a high cost of plasticizer because of the high price of catalyst used. In addition, although some enterprises have produced citrate plasticizers, users still choose cheap and familiar plasticizer products because they do not pay attention to the market promotion of products. It has become an inevitable trend to speed up the elimination of toxic plasticizers and develop and popularize new non-toxic plasticizers. Domestic production enterprises should vigorously study new catalysis and separation processes and bring a new generation of plasticizer products with higher cost performance, safety, reliability and environmental friendliness to the market as soon as possible.

4. Market segmentation according to application fields.

Plasticizer is the largest plastic additive. At present, there are more than 200 kinds of plasticizers in the world, each with its own physical and chemical properties and different application fields. After ten years' development, China's plasticizer industry has a considerable industrial base, and its production technology is not backward. Different products have different requirements for health and safety performance. Therefore, market segmentation according to application fields is an important means to avoid "trouble" of plasticizers. Plasticizer enterprises in China should pay more attention to the adaptability of different kinds of plasticizers in various products while increasing production. The two advantages are the most important, and the two disadvantages are the least. It provides guiding suggestions for users and proves to consumers that it is safe to use plasticizers reasonably with practice and facts.