JP2023094867A - Biomass plasticizer for vinyl chloride-based resin - Google Patents

Abstract

To provide a biomass plasticizer for a vinyl chloride-based resin which can impart excellent heat resistance and cold resistance to a molding of a vinyl chloride-based resin composition, and can suppress an emission amount of carbon dioxide by employing a biomass plasticizer obtained from a biomass-derived raw material.SOLUTION: A biomass plasticizer for a vinyl chloride-based resin contains component (A): one kind of 4-cyclohexene-1,2-dicarboxylic acid diester represented by general formula (1) or a mixture of two or more kinds of 4-cyclohexene-1,2-dicarboxylic acid diesters, and component (B): epoxidized vegetable oil, wherein a biomass degree of the component (A) is 50-100%, and a mass ratio of the component (A) to the component (B) is 50-99 mass%: 1-50 mass%. In the formula, R1 and R2 are the same or different, and represent a biomass-derived straight-chain alkyl group having 8 to 14 carbon atoms.SELECTED DRAWING: None

Description

The present invention relates to a biomass plasticizer for vinyl chloride resins.

Vinyl chloride resin (PVC) is one of the representative plastics, and has physical properties such as being inexpensive and excellent in heat resistance, and therefore has a wide variety of uses. Since vinyl chloride resin is hard and brittle, vinyl chloride resin is generally softened by adding a plasticizer before use.

As plasticizers used in vinyl chloride resins, higher alkyl esters of polybasic acids such as petroleum-derived phthalates, adipates, and trimellitates are known. Esters were often used.

In recent years, along with the increasing demand for building a recycling-oriented society, there is a desire to break away from petroleum-derived materials in the material field, and the use of biomass is attracting attention. Biomass is an organic compound that is photosynthesised from carbon dioxide and water, and is a so-called carbon-neutral material that regenerates carbon dioxide and water by using it. In recent years, the practical use of biomass chemical products using these biomass as raw materials has progressed rapidly, and attempts have been made to produce general-purpose chemicals from these biomass raw materials.

Patent Document 1 discloses isosorbide epoxy diesters as plasticizers for vinyl chloride resins. The plasticizer is a plasticizer using biomass-derived isosorbide and unsaturated fatty acid as raw materials. However, the plasticizer has insufficient performance as a plasticizer for vinyl chloride resins.

WO2016/046490

The problem to be solved by the present invention is that it is possible to impart excellent heat resistance and cold resistance to a molded product of a vinyl chloride resin composition, and to configure a biomass plasticizer obtained from a biomass-derived raw material. An object of the present invention is to provide a biomass plasticizer for vinyl chloride resins capable of suppressing carbon dioxide emissions.

In view of the current situation, the present inventors have made intensive studies to solve the above problems, and as a result, one or a mixture of two or more dicarboxylic acid diesters having a specific structure obtained from biomass-derived raw materials, epoxy A biomass plasticizer for vinyl chloride resin containing a modified vegetable oil and a biomass for vinyl chloride resin having a specific biomass degree that can impart excellent heat resistance and cold resistance to moldings of vinyl chloride resin compositions. The present inventors have found that it is a plasticizer and have completed the present invention.

That is, the present invention provides a biomass plasticizer for vinyl chloride resins having the following items.

［式中、Ｒ^１及びＲ^２は、同一又は異なって、それぞれ炭素数８～１４のバイオマス由来直鎖状アルキル基を示す。］
で表される４－シクロヘキセン－１，２－ジカルボン酸ジエステルの１種、又は２種以上の混合物、及び
（Ｂ）成分：エポキシ化植物油
を含有する塩化ビニル系樹脂用バイオマス可塑剤であって、
（Ａ）成分のバイオマス度が５０～１００％であり、かつ、（Ａ）成分と（Ｂ）成分の質量比が５０～９９質量％：１～５０質量％であることを特徴とする塩化ビニル系樹脂用バイオマス可塑剤。 [Section 1]
(A) Component:
General formula (1)

[In the formula, R ¹ and R ² are the same or different and each represent a biomass-derived linear alkyl group having 8 to 14 carbon atoms. ]
One or a mixture of two or more 4-cyclohexene-1,2-dicarboxylic acid diesters represented by and component (B): a biomass plasticizer for vinyl chloride resins containing epoxidized vegetable oil,
Vinyl chloride, wherein the component (A) has a biomass degree of 50 to 100%, and the mass ratio of the component (A) and the component (B) is 50 to 99% by mass: 1 to 50% by mass. Biomass plasticizer for system resins.

[Section 2]
The biomass plasticizer for vinyl chloride resins according to [Item 1], wherein the component (A) is di-n-octyl 4-cyclohexene-1,2-dicarboxylate.

[Section 3]
Component (A) is (a) di-n-octyl 4-cyclohexene-1,2-dicarboxylate, (b) 4-cyclohexene-1,2-dicarboxylic acid = n-octyl = n-dodecyl, and (c) 4 -cyclohexene-1,2-dicarboxylic acid = n-octyl = n-tetradecyl, (d) di-n-dodecyl 4-cyclohexene-1,2-dicarboxylic acid, (e) 4-cyclohexene-1,2-dicarboxylic acid = The biomass plasticizer for vinyl chloride resins according to [Item 1], wherein n-dodecyl=n-tetradecyl and (f) di-n-tetradecyl 4-cyclohexene-1,2-dicarboxylate.

[Section 4]
(A) component: the total of (a) to (f) is 100 mol%, and
(a): (b): (c): (d): (e): (f) = 20.0 to 67.2 mol%: 19.8 to 40.7 mol%: 5.7 to 11.8 mol% : 1.9-15.8 mol%: 1.1-9.2 mol%, : 0.1-1.4 mol%, the biomass plasticizer for vinyl chloride resin according to [3].

[Section 5]
(A) component: the total of (a) to (f) is 100 mol%, and
(a): (b): (c): (d): (e): (f) = 25.0 to 64.0 mol%: 24.8 to 38.8 mol%: 7.2 to 11.2 mol% : 2.4 to 15.0 mol%: 1.4 to 8.7 mol%, : 0.2 to 1.3 mol% for vinyl chloride resin according to [3] or [4] Biomass plasticizer.

[Item 6]
[Claim 1] to [Claim 5], wherein one kind of 4-cyclohexene-1,2-dicarboxylic acid diester represented by general formula (1) or a mixture of two or more kinds thereof has a biomass degree of 60 to 100%. Biomass plasticizer for vinyl chloride resin according to any one of.

[Item 7]
[Claim 1] to [Claim 6], wherein one kind of 4-cyclohexene-1,2-dicarboxylic acid diester represented by general formula (1) or a mixture of two or more kinds thereof has a biomass degree of 65 to 100%. Biomass plasticizer for vinyl chloride resin according to any one of.

[Item 8]
The biomass plasticizer for vinyl chloride resins according to any one of [1] to [7], wherein the epoxidized vegetable oil is epoxidized soybean oil and/or epoxidized linseed oil.

[Item 9]
A vinyl chloride resin composition comprising a vinyl chloride resin and the biomass plasticizer for vinyl chloride resin according to any one of [1] to [8].

[Item 10]
5 to 200 parts by mass of the biomass plasticizer for vinyl chloride resin according to any one of [Item 1] to [Item 8] with respect to 100 parts by mass of vinyl chloride resin [Item 9] ] The vinyl chloride-based resin composition according to .

[Item 11]
10 to 100 parts by mass of the biomass plasticizer for vinyl chloride resin according to any one of [Item 1] to [Item 8] with respect to 100 parts by mass of vinyl chloride resin [Item 9] ] or the vinyl chloride resin composition according to [Item 10].

[Item 12]
A molded article obtained from the vinyl chloride resin composition according to any one of [9] to [11].

By replacing the composition of plasticizers for vinyl chloride resins, which relied entirely on petroleum-derived plasticizers for vinyl chloride resins, with biomass plasticizers for vinyl chloride resins obtained from plant-derived raw materials, we will reduce the use of petroleum resources. The environmental load can be reduced by reducing the amount used and suppressing the amount of carbon dioxide emitted during the production of plasticizers for vinyl chloride resins. The biomass plasticizer for vinyl chloride resins of the present invention has excellent compatibility with vinyl chloride resins, so that it has excellent plasticization efficiency and flexibility, can impart excellent heat resistance and cold resistance, and is capable of imparting specific biomass It can be suitably used as a plasticizer having a degree of

［式中、Ｒ^１及びＲ^２は、同一又は異なって、それぞれ炭素数８～１４のバイオマス由来直鎖状アルキル基を示す。］
で表される４－シクロヘキセン－１，２－ジカルボン酸ジエステルの１種、又は２種以上の混合物、及び
（Ｂ）成分：エポキシ化植物油
を含有する塩化ビニル系樹脂用バイオマス可塑剤であって、
（Ａ）成分のバイオマス度が５０～１００％であり、かつ（Ａ）成分と（Ｂ）成分の質量比が５０～９９質量％：１～５０質量％であることを特徴とする。 The biomass plasticizer for vinyl chloride resins of the present invention is
(A) Component:
General formula (1)

[In the formula, R ¹ and R ² are the same or different and each represent a biomass-derived linear alkyl group having 8 to 14 carbon atoms. ]
One or a mixture of two or more 4-cyclohexene-1,2-dicarboxylic acid diesters represented by and component (B): a biomass plasticizer for vinyl chloride resins containing epoxidized vegetable oil,
The biomass degree of component (A) is 50 to 100%, and the mass ratio of component (A) to component (B) is 50 to 99% by mass: 1 to 50% by mass.

Specific examples of R ¹ and R ² in the 4-cyclohexene-1,2-dicarboxylic acid diester represented by general formula (1) are the same or different and include a biomass-derived n-octyl group and n-nonyl. group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, preferably n-octyl group, n-decyl group, n-dodecyl group, n- A tetradecyl group, particularly preferably an n-octyl group, an n-dodecyl group, or an n-tetradecyl group.

R ¹ and R ² of the 4-cyclohexene-1,2-dicarboxylic acid diester represented by the general formula (1) are the same or different, and are each a biomass-derived linear alkyl group having 1 to 7 carbon atoms. In this case, the heat resistance (volatilization loss) deteriorates, which is not preferable.

When R ¹ and R ² in the 4-cyclohexene-1,2-dicarboxylic acid diester represented by the general formula (1) are the same or different and each is a biomass-derived linear alkyl group having 15 or more carbon atoms is not preferable because the cold resistance (softening temperature) deteriorates.

The description of the mixed-group ester of the 4-cyclohexene-1,2-dicarboxylic acid diester represented by the general formula (1) in which R ¹ and R ² are different is described in the following formula (2) where R ¹ is n- When an octyl group and R ² is an n-dodecyl group, 4-cyclohexene-1,2-dicarboxylic acid = n-octyl = n-dodecyl shall be described in the present specification and claims.

Specific examples of 4-cyclohexene-1,2-dicarboxylic acid diesters represented by general formula (1) include di-n-octyl 4-cyclohexene-1,2-dicarboxylate, 4-cyclohexene-1, di-n-decyl 2-dicarboxylate, di-n-dodecyl 4-cyclohexene-1,2-dicarboxylate, and di-n-tetradecyl 4-cyclohexene-1,2-dicarboxylate, preferably 4-cyclohexene- It is di-n-octyl 1,2-dicarboxylate.

Specific examples of mixtures of two or more 4-cyclohexene-1,2-dicarboxylic acid diesters represented by general formula (1) include di-n-octyl 4-cyclohexene-1,2-dicarboxylate and 4-cyclohexene. -mixture of di-n-decyl 1,2-dicarboxylate, di-n-octyl 4-cyclohexene-1,2-dicarboxylate, mixture of di-n-dodecyl 4-cyclohexene-1,2-dicarboxylate, 4-cyclohexene- Mixture of di-n-octyl 1,2-dicarboxylate, di-n-tetradecyl 4-cyclohexene-1,2-dicarboxylate, di-n-decyl 4-cyclohexene-1,2-dicarboxylate, 4-cyclohexene-1,2 -mixture of di-n-dodecyl dicarboxylate, di-n-decyl 4-cyclohexene-1,2-dicarboxylate, mixture of di-n-tetradecyl 4-cyclohexene-1,2-dicarboxylate, 4-cyclohexene-1,2- A mixture of di-n-dodecyl dicarboxylate, di-n-tetradecyl 4-cyclohexene-1,2-dicarboxylate, di-n-octyl 4-cyclohexene-1,2-dicarboxylate, di-4-cyclohexene-1,2-dicarboxylate Mixture of n-decyl, di-n-dodecyl 4-cyclohexene-1,2-dicarboxylate, di-n-octyl 4-cyclohexene-1,2-dicarboxylate, di-n-dodecyl 4-cyclohexene-1,2-dicarboxylate , a mixture of di-n-tetradecyl 4-cyclohexene-1,2-dicarboxylate, di-n-decyl 4-cyclohexene-1,2-dicarboxylate, di-n-dodecyl 4-cyclohexene-1,2-dicarboxylate, 4- Mixture of di-n-tetradecyl cyclohexene-1,2-dicarboxylate, di-n-octyl 4-cyclohexene-1,2-dicarboxylate, di-n-decyl 4-cyclohexene-1,2-dicarboxylate, 4-cyclohexene-1 , di-n-dodecyl 2-dicarboxylate, di-n-tetradecyl 4-cyclohexene-1,2-dicarboxylate, di-n-octyl 4-cyclohexene-1,2-dicarboxylate, 4-cyclohexene-1,2- a mixture of dicarboxylic acid = n-octyl = n-decyl and di-n-decyl 4-cyclohexene-1,2-dicarboxylate, di-n-octyl 4-cyclohexene-1,2-dicarboxylate, 4-cyclohexene-1, Mixture of 2-dicarboxylic acid = n-octyl = n-dodecyl and di-n-dodecyl 4-cyclohexene-1,2-dicarboxylate, di-n-octyl 4-cyclohexene-1,2-dicarboxylate, 4-cyclohexene- mixture of 1,2-dicarboxylic acid = n-octyl = n-tetradecyl and di-n-tetradecyl 4-cyclohexene-1,2-dicarboxylate, di-n-decyl 4-cyclohexene-1,2-dicarboxylate, 4- a mixture of cyclohexene-1,2-dicarboxylic acid = n-decyl = n-dodecyl and di-n-dodecyl 4-cyclohexene-1,2-dicarboxylate, di-n-decyl 4-cyclohexene-1,2-dicarboxylate, A mixture of 4-cyclohexene-1,2-dicarboxylic acid = n-decyl = n-tetradecyl and 4-cyclohexene-1,2-dicarboxylic acid di-n-tetradecyl, 4-cyclohexene-1,2-dicarboxylic acid di-n- A mixture of dodecyl, 4-cyclohexene-1,2-dicarboxylic acid = n-dodecyl = n-tetradecyl, and 4-cyclohexene-1,2-dicarboxylic acid di-n-tetradecyl, 4-cyclohexene-1,2-dicarboxylic acid di n-octyl, 4-cyclohexene-1,2-dicarboxylic acid = n-octyl = n-decyl, 4-cyclohexene-1,2-dicarboxylic acid = n-octyl = n-dodecyl, 4-cyclohexene-1,2- di-n-decyl dicarboxylate, 4-cyclohexene-1,2-dicarboxylic acid=n-decyl=n-dodecyl, and a mixture of di-n-dodecyl 4-cyclohexene-1,2-dicarboxylate, 4-cyclohexene-1, 2-dicarboxylic acid di-n-octyl, 4-cyclohexene-1,2-dicarboxylic acid = n-octyl = n-dodecyl, 4-cyclohexene-1,2-dicarboxylic acid = n-octyl = n-tetradecyl, 4-cyclohexene mixture of di-n-dodecyl-1,2-dicarboxylate, n-dodecyl-n-tetradecyl 4-cyclohexene-1,2-dicarboxylate, and di-n-tetradecyl 4-cyclohexene-1,2-dicarboxylate, 4 -cyclohexene-1,2-dicarboxylic acid di-n-decyl, 4-cyclohexene-1,2-dicarboxylic acid = n-decyl = n-dodecyl, 4-cyclohexene-1,2-dicarboxylic acid = n-decyl = n- Tetradecyl, 4-cyclohexene-1,2-dicarboxylic acid di-n-dodecyl, 4-cyclohexene-1,2-dicarboxylic acid = n-dodecyl = n-tetradecyl, and 4-cyclohexene-1,2-dicarboxylic acid di-n- mixture of tetradecyl, 4-cyclohexene-1,2-dicarboxylic acid di-n-octyl, 4-cyclohexene-1,2-dicarboxylic acid = n-octyl = n-decyl, 4-cyclohexene-1,2-dicarboxylic acid = n -octyl = n-dodecyl, 4-cyclohexene-1,2-dicarboxylic acid = n-octyl = n-tetradecyl, 4-cyclohexene-1,2-dicarboxylic acid di-n-decyl, 4-cyclohexene-1,2-dicarboxylic acid acid = n-decyl = n-dodecyl, 4-cyclohexene-1,2-dicarboxylic acid = n-decyl = n-tetradecyl, 4-cyclohexene-1,2-dicarboxylic acid di-n-dodecyl, 4-cyclohexene-1, Mixtures of 2-dicarboxylic acid=n-dodecyl=n-tetradecyl and di-n-tetradecyl 4-cyclohexene-1,2-dicarboxylic acid are included.

Among the specific examples of the mixture of two or more 4-cyclohexene-1,2-dicarboxylic acid diesters, preferably (a) di-n-octyl 4-cyclohexene-1,2-dicarboxylate, (b) 4- Cyclohexene-1,2-dicarboxylic acid = n-octyl = n-dodecyl, (c) 4-cyclohexene-1,2-dicarboxylic acid = n-octyl = n-tetradecyl, (d) 4-cyclohexene-1,2- a mixture of di-n-dodecyl dicarboxylate, (e) 4-cyclohexene-1,2-dicarboxylic acid=n-dodecyl=n-tetradecyl, and (f) di-n-tetradecyl 4-cyclohexene-1,2-dicarboxylate be.

Among the specific examples of the mixture of two or more 4-cyclohexene-1,2-dicarboxylic acid diesters, preferably the total amount of the diester mixture of (a) to (f) is 100 mol%, and (a): (b): (c): (d): (e): (f) = 20.0 to 67.2 mol%: 19.8 to 40.7 mol%: 5.7 to 11.8 mol%: 1.9 15.8 mol%: 1.1-9.2 mol%, : 0.1-1.4 mol%, particularly preferably the total of the diester mixture of (a) to (f) is 100 mol %, and (a): (b): (c): (d): (e): (f) = 25.0 to 64.0 mol%: 24.8 to 38.8 mol%: 7.2 to 11.2 mol %: 2.4-15.0 mol %: 1.4-8.7 mol %, : 0.2-1.3 mol %.

One of the 4-cyclohexene-1,2-dicarboxylic acid diesters represented by the general formula (1), or a mixture of two or more of them, is limited particularly by its production method as long as it satisfies performance as a plasticizer. 4-cyclohexene-1,2-dicarboxylic acid or anhydride thereof derived from petroleum and/or biomass raw materials, and linear aliphatic saturated alcohols derived from biomass having 8 to 14 carbon atoms, although not intended to be can be easily obtained by adding one or two or more of them and subjecting them to an esterification reaction by a known method.

In the esterification, a water entraining agent such as benzene, toluene, xylene, cyclohexane, etc. can be used in order to promote the distillation of water produced by the reaction.

In addition, if oxygen-containing organic compounds such as oxides, peroxides, and carbonyl compounds are generated due to oxidative deterioration of the diester compound and organic solvent (water entraining agent) during the esterification reaction, heat resistance, weather resistance, etc. will be adversely affected. It is desirable to carry out the reaction in the system under an atmosphere of an inert gas such as nitrogen gas or under an inert gas stream under normal pressure or reduced pressure. After completion of the esterification reaction, it is recommended to distill off excess raw materials under reduced pressure or normal pressure.

The diester compound according to the present invention obtained by the above esterification method is subsequently subjected to basic treatment (neutralization treatment) as necessary, followed by water washing treatment, liquid-liquid extraction, distillation (reduced pressure, dehydration treatment), adsorption purification treatment, etc. It may be purified by

The base used for the base treatment is not particularly limited as long as it is a basic compound, and examples thereof include sodium hydroxide and sodium carbonate.

Examples of adsorbents used for adsorption purification include activated carbon, activated clay, activated alumina, hydrotalcite, silica gel, silica alumina, zeolite, magnesia, calcia, and diatomaceous earth. They can be used singly or in combination of two or more.

The above treatment may be carried out at room temperature, but may also be carried out by heating to about 40 to 90°C.

The biomass degree of diester is measured by burning a sample to be measured to generate carbon dioxide, and reducing the carbon dioxide purified in a vacuum line with hydrogen using iron as a catalyst to generate graphite. Then, this graphite is mounted on a tandem accelerator-based ¹⁴ C-AMS dedicated device (manufactured by NEC) to count ¹⁴ C, the concentration of ¹³ C ( ¹³ C/ ¹² C), the concentration of ¹⁴ C ( ¹⁴ C/ ¹² C) is measured and from this measurement the ratio of ¹⁴ C concentration of sample carbon to standard modern carbon is calculated. In this measurement, oxalic acid (HOxII) provided by the US National Institute of Standards (NIST) was used as a standard sample.

From the viewpoint of reducing the amount of petroleum resources used and reducing the environmental load, the biomass degree of one or a mixture of two or more 4-cyclohexene-1,2-dicarboxylic acid diesters represented by the general formula (1) is The higher the value, the better, and the environmental load can be reduced by suppressing the amount of carbon dioxide emitted during the production of plasticizers for vinyl chloride resins. From the viewpoint of practicality such as convenience, the biomass degree of one or a mixture of two or more 4-cyclohexene-1,2-dicarboxylic acid diesters represented by the general formula (1) is preferably 50 to 100. %, more preferably 60 to 100%, and particularly preferably 65 to 100%. If the biomass degree of one of the 4-cyclohexene-1,2-dicarboxylic acid diesters represented by the general formula (1) or a mixture of two or more of them is less than 50%, dioxide during the production of plasticizers for vinyl chloride resins It is not preferable because it makes little contribution to reducing carbon emissions.

Maleic anhydride, which is a raw material for 4-cyclohexene-1,2-dicarboxylic acid or its anhydride, is also disclosed, for example, in Y.K. Tachibana, S.; kimura, K.; Kasuya, Sci. Rep. , 5, 8249 (2015). Maleic anhydride can be produced from biomass-derived furfural by the known method described in . The maleic anhydride thus obtained has a biomass degree of 99% or more.

Furthermore, butadiene, which is a raw material for 4-cyclohexene-1,2-dicarboxylic acid or its anhydride, can also be produced from ethanol derived from biomass materials by a known method described in JP-A-2019-090061. can be done. The biomass degree of the butadiene thus obtained is 99% or more.

4-Cyclohexene-1,2-dicarboxylic acid derived from a biomass material or its anhydride can be produced by, for example, the known Diels-Alder reaction using maleic anhydride and butadiene described above. The biomass degree of 4-cyclohexene-1,2-dicarboxylic acid or its anhydride thus obtained is 99% or more.

By performing an esterification reaction of biomass raw material-derived 4-cyclohexene-1,2-dicarboxylic acid or its anhydride and a biomass raw material-derived linear aliphatic saturated alcohol having 8 to 14 carbon atoms by a known method, the present invention can be obtained. 4-Cyclohexene-1,2-dicarboxylic acid diesters according to the invention can be produced. The biomass degree of the 4-cyclohexene-1,2-dicarboxylic acid diester thus obtained is 99% or more.

Further, instead of using biomass raw material-derived 4-cyclohexene-1,2-dicarboxylic acid or its anhydride, for example, petroleum-derived butadiene and petroleum-derived 4-cyclohexene-1,2-dicarboxylic acid produced from petroleum-derived maleic anhydride A dicarboxylic acid or its anhydride can also be used as a raw material. The biomass degree of petroleum-derived 4-cyclohexene-1,2-dicarboxylic acid or its anhydride is less than 1%.

Biomass raw material-derived linear aliphatic saturated alcohols having 8 to 14 carbon atoms are generally alcohol mixtures obtained by hydrogenation reduction of fatty acid methyl derived from natural oils such as coconut oil and palm kernel oil. The 4-cyclohexene-1,2-dicarboxylic acid diester represented by the formula (1) can be used as a raw material for one or a mixture of two or more of them, and the alcohol mixture is separated and purified by distillation or the like. The alcohol thus obtained can also be used as a starting material for one or a mixture of two or more of the 4-cyclohexene-1,2-dicarboxylic acid diesters represented by the general formula (1).

A biomass raw material-derived linear aliphatic saturated alcohol having 8 to 14 carbon atoms is used as a raw material for one or a mixture of two or more 4-cyclohexene-1,2-dicarboxylic acid diesters represented by the general formula (1). As, one or two or more can be used. The biomass degree of the biomass raw material-derived linear aliphatic saturated alcohol having 8 to 14 carbon atoms is 99% or more.

Instead of using biomass raw material-derived 4-cyclohexene-1,2-dicarboxylic acid or its anhydride, petroleum-derived 4-cyclohexene-1,2-dicarboxylic acid or its anhydride and C 8-14 biomass raw material-derived The 4-cyclohexene-1,2-dicarboxylic acid diester according to the present invention can be produced by subjecting it to an esterification reaction with a chain aliphatic saturated alcohol by a known method. The biomass degree of the 4-cyclohexene-1,2-dicarboxylic acid diester thus obtained is 67% to 78%.

The acid value of one of the 4-cyclohexene-1,2-dicarboxylic acid diesters represented by the general formula (1) or a mixture of two or more of them is preferably 0.1 mgKOH/g or less, more preferably 0.1 mgKOH/g or less. 05 mgKOH/g or less, particularly preferably 0.01 mgKOH/g or less. When the acid value is 0.1 mgKOH/g or less, the heat resistance of one or a mixture of two or more 4-cyclohexene-1,2-dicarboxylic acid diesters represented by the general formula (1) tends to be further improved. is recognized, and such a preferable range has a favorable effect on improving the thermal oxidation stability of the biomass plasticizer for vinyl chloride resins of the present invention.

As the epoxidized vegetable oil according to the present invention, for example, an epoxidized vegetable oil obtained by epoxidizing a vegetable oil can be used, and examples thereof include epoxidized vegetable oils such as epoxidized soybean oil and epoxidized linseed oil. Soybean oil, epoxidized linseed oil, and particularly preferably epoxidized soybean oil. The biomass degree of the epoxidized vegetable oil according to the present invention is 99% or more. As the epoxidized vegetable oil according to the present invention, one kind or a mixture of two or more kinds may be used.

The biomass plasticizer for vinyl chloride resins of the present invention is one or a mixture of two or more 4-cyclohexene-1,2-dicarboxylic acid diesters represented by general formula (1) having a specific degree of biomass. , and epoxidized vegetable oil in specific mass ratios. In the present specification and claims, the degree of biomass is a value measured by the method described in Examples below.

The mass ratio of the (A) component and the (B) component contained in the biomass plasticizer for vinyl chloride resin of the present invention is, (A) component: (B) component = 50 to 99% by mass: 1 to 50% by mass. be.

<Vinyl chloride resin>
The vinyl chloride resin used in the present invention is a homopolymer of vinyl chloride or vinylidene chloride and a copolymer of vinyl chloride or vinylidene chloride. In the case of vinyl resins, a method of suspension polymerization in the presence of an oil-soluble polymerization catalyst is exemplified, and in the case of vinyl chloride paste resins, a method of emulsion polymerization in an aqueous medium in the presence of a water-soluble polymerization catalyst is exemplified. The degree of polymerization of these vinyl chloride resins is generally 300-5000, preferably 400-3500, more preferably 700-3000. If the degree of polymerization is too low, the heat resistance tends to deteriorate, and if it is too high, the moldability tends to deteriorate.

In the case of copolymers, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1- α-olefins having 2 to 30 carbon atoms such as tridecene and 1-tetradecene, acrylic acid and its esters, methacrylic acid and its esters, maleic acid and its esters, vinyl acetate, vinyl propionate, alkyl vinyl ethers, etc. Vinyl compounds, multifunctional monomers such as diallyl phthalate, copolymers of these and vinyl chloride monomers, ethylene-acrylic acid ester copolymers such as ethylene-ethyl acrylate copolymers, ethylene-methacrylic acid ester copolymers Polymer, ethylene-vinyl acetate copolymer (EVA), chlorinated polyethylene, butyl rubber, crosslinked acrylic rubber, polyurethane, butadiene-styrene-methyl methacrylate copolymer (MBS), butadiene-acrylonitrile-(α-methyl)styrene copolymer Polymer (ABS), styrene-butadiene copolymer, polyethylene, polymethyl methacrylate, and a graft copolymer obtained by grafting a vinyl chloride monomer to a mixture thereof are exemplified.

<Vinyl chloride resin composition>
The content of the biomass plasticizer for vinyl chloride resin in the vinyl chloride resin composition of the present invention is appropriately selected according to its application, but is usually 5 to 200 parts per 100 parts by mass of the vinyl chloride resin. parts by mass, preferably 10 to 100 parts by mass. If the amount is less than 5 parts by mass, it is difficult to obtain the desired plasticizing effect, and if the amount exceeds 200 parts by mass, bleeding to the surface of the molded article is severe. However, when a filler or the like is added to the above vinyl chloride resin composition, the plasticizer can be blended beyond the above range because the filler itself absorbs oil. For example, when 100 parts by mass of calcium carbonate as a filler is blended with 100 parts by mass of vinyl chloride resin, about 1 to 500 parts by mass of the plasticizer can be blended.

In the vinyl chloride resin composition of the present invention, other known plasticizers can be used together with the biomass plasticizer for vinyl chloride resins. In addition, if necessary, stabilizers, stabilizing aids, antioxidants (antiaging agents), ultraviolet absorbers, hindered amine light stabilizers, fillers, diluents, viscosity reducers, thickeners, processing aids Additives such as agents, lubricants, antistatic agents, flame retardants, foaming agents, adhesives and coloring agents can be added.

Plasticizers and additives other than the biomass plasticizer for vinyl chloride resins according to the present invention may be blended together with the biomass plasticizer for vinyl chloride resins in combination of one or more.

Examples of known plasticizers that can be used in combination with the biomass plasticizer for vinyl chloride resins according to the present invention include benzoic acid esters such as diethylene glycol dibenzoate, dibutyl phthalate (DBP), and di-2-phthalate. Ethylhexyl (DOP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), diundecyl phthalate (DUP), ditridecyl phthalate (DTDP), bis(2-ethylhexyl) terephthalate (DOTP), bis(2 -ethylhexyl) (DOIP), di-2-ethylhexyl adipate (DOA), diisononyl adipate (DINA), diisodecyl adipate (DIDA), di-2-ethylhexyl sebacate (DOS), sebacin aliphatic dibasic acid esters such as diisononyl acid (DINS), trimellitate esters such as tri-2-ethylhexyl trimellitate (TOTM), triisononyl trimellitate (TINTM), triisodecyl trimellitate (TIDTM), Pyromellitic acid esters such as tetra-2-ethylhexyl pyromellitic acid (TOPM), phosphates such as tri-2-ethylhexyl phosphate (TOP) and tricresyl phosphate (TCP), polyhydric alcohols such as pentaerythritol alkyl esters, polyesters with a molecular weight of 800 to 4000 synthesized by polyesterification of a dibasic acid such as adipic acid and glycol, 4,5-epoxy-1,2-cyclohexanedicarboxylic acid di-2-ethylhexyl ester, etc. Alicyclic dibasic acid esters such as epoxy esters, diisononyl 1,2-cyclohexanedicarboxylate (DINCH), and di-2-ethylhexyl 4-cyclohexene-1,2-dicarboxylate (general formula according to the present invention ( 1) excluding one or a mixture of two or more of 4-cyclohexene-1,2-dicarboxylic acid diesters represented by ), fatty acid glycol esters such as 1,4-butanediol dicaprate, tributyl acetylcitrate Citrate esters such as (ATBC), acetyl trihexyl citrate (ATHC), acetyl trihexyl citrate (ATEHC), butyryl trihexyl citrate (BTHC), isosorbide diesters, chlorine obtained by chlorinating paraffin wax and n-paraffin Examples include paraffins, chlorinated fatty acid esters such as chlorinated stearate, and higher fatty acid esters such as butyl oleate. When the plasticizer that can be used in combination is blended, the recommended blending amount is about 1 to 100 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.

Stabilizers include lithium stearate, magnesium stearate, magnesium laurate, calcium ricinoleate, calcium stearate, barium laurate, barium ricinoleate, barium stearate, zinc octylate, zinc laurate, zinc ricinoleate, stearic acid. Metal soap compounds such as zinc, organic tin compounds such as dimethyltin bis-2-ethylhexylthioglycolate, dibutyltin maleate, dibutyltin bisbutyl maleate and dibutyltin dilaurate, and antimony mercaptide compounds are exemplified. When a stabilizer is blended, it is recommended that the stabilizer be added in an amount of about 0.1 to 20 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.

Among the stabilizers, a combination of calcium stearate and zinc stearate is most preferably used from the viewpoint of safety. In addition, it is recommended that the total amount of the compound is 0.1 to 10 parts by mass, preferably 0.2 to 6 parts by mass, based on 100 parts by mass of the vinyl chloride resin. Although there is no particular limitation as long as the range exhibits the effect of , it is usually used in the range of 5:1 to 1:5.

Stabilizing aids include phosphite compounds such as triphenylphosphite, monooctyldiphenylphosphite and tridecylphosphite, beta-diketone compounds such as acetylacetone and benzoylacetone, glycerin, sorbitol, pentaerythritol, polyethylene glycol and the like. Examples include polyol compounds, perchlorate compounds such as barium perchlorate and sodium perchlorate, hydrotalcite compounds, and zeolites. When a stabilizing aid is blended, it is recommended that the amount of the stabilizing aid blended with respect to 100 parts by mass of the vinyl chloride resin be about 0.1 to 20 parts by mass.

Antioxidants include 2,6-di-tert-butylphenol, tetrakis[methylene-3-(3,5-tert-butyl-4-hydroxyphenol)propionate]methane, 2-hydroxy-4-methoxybenzophenone, and the like. Phenolic compounds, alkyl disulfides, thiodipropionate esters, sulfur compounds such as benzothiazole, trisnonylphenyl phosphite, diphenyl isodecyl phosphite, triphenyl phosphite, tris(2,4-di-tert-butylphenyl ) phosphoric acid compounds such as phosphite, and organometallic compounds such as zinc dialkyldithiophosphate and zinc diaryldithiophosphate. When an antioxidant is blended, it is recommended that the amount of the antioxidant to be blended is about 0.2 to 20 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.

UV absorbers include salicylate compounds such as phenyl salicylate and p-tert-butylphenyl salicylate; benzophenone compounds such as 2-hydroxy-4-n-octoxybenzophenone and 2-hydroxy-4-n-methoxybenzophenone; Examples include benzotriazole compounds such as 5-methyl-1H-benzotriazole and 1-dioctylaminomethylbenzotriazole, and cyanoacrylate compounds. When an ultraviolet absorber is blended, it is recommended that the amount of the ultraviolet absorber to be blended is about 0.1 to 10 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.

Hindered amine light stabilizers include bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1 , 2,2,6,6-pentamethyl-4-piperidyl sebacate (mixture), bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1- dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate, decanedioic acid bis(2,2,6,6-tetramethyl-1(octyloxy)-4-piperidyl) ester and 1,1-dimethylethyl Reaction products of hydroperoxide and octane, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 2,2,6,6-tetramethyl-4-piperidinol and ester mixtures of higher fatty acids, tetrakis(2 ,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2 ,3,4-butane tetracarboxylate, polycondensation product of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol, poly[{(6-(1,1,3 ,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl){(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethylene {(2,2, 6,6-tetramethyl-4-piperidyl)imino}}, dibutylamine/1,3,5-triazine/N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl-1, Polycondensate of 6-hexamethylenediamine and N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine, N,N',N'',N'''-tetrakis-(4,6 -bis-(butyl-(N-methyl-2,2,6,6-tetramethylpiperidin-4-yl)amino)-triazin-2-yl)-4,7-diazadecane-1,10-diamine and the like When a light stabilizer is blended, it is recommended that the amount of the light stabilizer to be added is about 0.1 to 10 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.

Fillers include metal oxides such as calcium carbonate, silica, alumina, clay, talc, diatomaceous earth, and ferrite, fibers and powders such as glass, carbon, and metals, glass spheres, graphite, aluminum hydroxide, barium sulfate, and magnesium oxide. , magnesium carbonate, magnesium silicate, and calcium silicate. When a filler is blended, it is recommended that the amount of the filler to be blended is about 1 to 100 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.

Examples of diluents include 2,2,4-trimethyl-1,3-pentanediol diisobutyrate and low-boiling aliphatic and aromatic hydrocarbons. When a diluent is added, it is recommended that the diluent be added in an amount of about 1 to 50 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.

Viscosity reducing agents include various nonionic surfactants, sulfosuccinate anionic surfactants, silicone compounds with surface activity, soybean oil lecithin, monohydric alcohols, glycol ethers, polyethylene glycols, etc. is exemplified. When a viscosity reducing agent is blended, it is recommended that the amount of the viscosity reducing agent to be blended is about 0.1 to 20 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.

Thickeners include synthetic fine silica powder, bentonite, ultrafine precipitated calcium carbonate, metal soap, hydrogenated castor oil, polyamide wax, polyethylene oxide, vegetable oil, particulate ester surfactant, and nonionic surfactant. An active agent etc. are illustrated. When a thickening agent is added, it is recommended that the amount of the thickening agent to be blended is about 1 to 50 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.

Examples of processing aids include liquid paraffin, polyethylene wax, stearic acid, stearamide, ethylene bis stearamide, butyl stearate, and calcium stearate. When a processing aid is blended, it is recommended that the amount of the processing aid to be blended is about 0.1 to 20 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.

Examples of lubricants include silicone, liquid paraffin, paraffin wax, fatty acid metal salts such as metal stearate and metal laurate, fatty acid amides, fatty acid waxes, and higher fatty acid waxes. When a lubricant is blended, it is recommended that the amount of the lubricant to be blended is about 0.1 to 10 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.

Examples of antistatic agents include alkylsulfonate-type, alkylethercarboxylic acid-type or dialkylsulfosuccinate-type anionic antistatic agents, nonionic antistatic agents such as polyethylene glycol derivatives, sorbitan derivatives, and diethanolamine derivatives, alkylamidoamine-type, alkyl Cationic antistatic agents such as dimethylbenzyl-type quaternary ammonium salts, alkylpyridinium-type organic acid salts or hydrochlorides, and amphoteric antistatic agents such as alkylbetaine-type and alkylimidazoline-type antistatic agents are exemplified. When an antistatic agent is added, it is recommended that the antistatic agent be added in an amount of about 0.1 to 10 parts by mass per 100 parts by mass of the vinyl chloride resin.

Flame retardants include inorganic compounds such as aluminum hydroxide, antimony trioxide, magnesium hydroxide, and zinc borate; Phosphorus compounds, halogen compounds such as chlorinated paraffin, and the like are exemplified. When a flame retardant is added, it is recommended that the flame retardant be added in an amount of about 0.1 to 20 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.

Examples of foaming agents include organic foaming agents such as azodicarbonamide and oxybisbenzenesulfonyl hydrazide, and inorganic foaming agents such as sodium bicarbonate. When a foaming agent is blended, it is recommended that the amount of the foaming agent to be blended is about 0.1 to 30 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.

Examples of coloring agents include carbon black, lead sulfide, white carbon, titanium white, lithopone, safflower, antimony sulfide, chrome yellow, chrome green, phthalocyanine green, cobalt blue, phthalocyanine blue, and molybdenum orange. When a coloring agent is blended, it is recommended that the amount of the coloring agent blended is about 1 to 100 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.

The vinyl chloride resin composition of the present invention is prepared by mixing the biomass plasticizer for vinyl chloride resin of the present invention, the vinyl chloride resin, and various additives as necessary in, for example, a handling mixer, a pony mixer, a butterfly mixer, a planetary mixer, Dissolvers, twin-screw mixers, three-roll mills, mortar mixers, Henschel mixers, Banbury mixers, ribbon blenders, conical twin-screw extruders, parallel twin-screw extruders, single-screw extruders, co-kneaders, Stir-mixing and melt-mixing can be performed by a kneader such as a roll kneader to obtain a powdery, pellet-like or paste-like vinyl chloride resin composition.

<Vinyl chloride resin molding>
The vinyl chloride resin composition of the present invention can be used for vacuum molding, compression molding, extrusion molding, injection molding, calendar molding, press molding, blow molding, powder molding, spread coating, dip coating, spray coating, paper casting, and extrusion coating. , gravure printing, screen printing, slush molding, rotational molding, cast molding, dip molding, welding, and the like, and can be molded into a desired shape.

The shape of the molded article is not particularly limited, but may be, for example, rod-shaped, sheet-shaped, film-shaped, plate-shaped, cylindrical, circular, elliptical, or special shapes such as toys or ornaments, such as star-shaped, A polygonal shape is exemplified.

<Evaluation of vinyl chloride resin molding>
(a) Softening temperature The softening temperature of the vinyl chloride sheet containing the vinyl chloride resin plasticizer is preferably -25°C or lower, more preferably -30°C or lower. In this specification, the softening temperature is a value measured by the method described in Examples below.

(b) Volatile Loss The volatile loss of the vinyl chloride sheet containing the vinyl chloride resin plasticizer is preferably less than 15%, more preferably less than 13%. In addition, in this specification, the amount of volatility is a value measured by the method described in the examples below.

(c) Heat resistance (sheet coloration) evaluation Heat resistance (sheet coloration) evaluation (170°C, 60 minutes) of a vinyl chloride sheet containing a vinyl chloride resin plasticizer is preferably slightly colored, more preferably No coloring. The term "heat resistance (sheet coloring)" as used herein is a value measured by the method described in Examples below.

(d) Evaluation of vinyl chloride sheet Evaluation of a vinyl chloride sheet containing a plasticizer for vinyl chloride resin is as follows: flexible temperature -25°C or less, volatility loss less than 13%, no sheet coloring; flexible temperature -30°C or less; Volatile loss less than 15%, no sheet coloring; Flexibility temperature -30°C or less, volatility loss less than 15%, sheet slightly colored; , No sheet coloring; is evaluated as particularly good.

The vinyl chloride sheet containing the biomass plasticizer for vinyl chloride resin of the present invention has a low softening temperature, a low volatility loss (170 ° C., 120 minutes), and has no sheet coloration, and a specific biomass degree Since it has, it is useful as a biomass plasticizer for vinyl chloride resins.

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. The abbreviations of the compounds in Examples and Comparative Examples and the measurement of each property are as follows.

<Compound used>
・ 4-Cyclohexene-1,2-dicarboxylic anhydride: manufactured by Shin Nippon Rika Co., Ltd., product name “Likacid TH” (biomass degree: less than 1%)
・ n-octanol: manufactured by New Japan Chemical Co., Ltd., product name “Conol 10WS” (biomass degree: 99% or more)
・ n-dodecanol: manufactured by New Japan Chemical Co., Ltd., product name “Conol 20P” (biomass degree: 99% or more)
・ n-tetradecanol: manufactured by New Japan Chemical Co., Ltd., product name “Conol 1495” (biomass degree: 99% or more)
・ Epoxidized soybean oil: manufactured by New Japan Chemical Co., Ltd., product name “Sanso Cizer E-2000H” (biomass degree: 99% or more)
・ Vinyl chloride resin: manufactured by Shin-Daiichi Vinyl Co., Ltd., product name “Zest1000Z” (straight, polymerization degree 1050)
・ DOP: New Japan Chemical Co., Ltd., product name “Sanso Cizer DOP” (di-2-ethylhexyl phthalate) (biomass degree: less than 1%)
・ DINP: Shin Nippon Rika Co., Ltd., product name “Sanso Cizer DINP” (diisononyl phthalate) (biomass degree: less than 1%)
・ DOTH: Shin Nippon Rika Co., Ltd., product name “Sanso Cizer DOTH” (di-2-ethylhexyl 4-cyclohexene-1,2-dicarboxylate) (biomass degree: less than 1%)

(1) Evaluation of physical properties of diester One or a mixture of two or more 4-cyclohexene-1,2-dicarboxylic acid diesters represented by the general formula (1) according to the present invention obtained in the following production examples , was analyzed by the following method.
Acid value: Measured according to JISK-0070 (1992).
Hue: Measured according to JISK-4101 (Hazen) (1995).

(2) Gas chromatography analysis (hereinafter abbreviated as GC analysis)
Model: Gas chromatograph GC-2025 (manufactured by Shimadzu Corporation)
Detector: FID
Column: Capillary column ZB-130m
Column temperature: from 60°C to 290°C, heating rate = 13°C/min, hold for 23 minutes Carrier gas: helium split ratio: 1:80
Sample: 50% acetone solution Injection volume: 0.5 µl
Quantification: DOP was used as an internal standard for quantification.

(3) Preparation of vinyl chloride press sheet 100 parts by mass of vinyl chloride resin (straight, polymerization degree 1050, product name “Zest1000Z”, manufactured by Shin-Daiichi Vinyl Co., Ltd.), calcium stearate (Nacalai Tesque Co., Ltd.) as a stabilizer ) and zinc stearate (manufactured by Nacalai Tesque Co., Ltd.) were blended in 0.3 and 0.2 parts by mass, respectively, stirred and mixed with a mortar mixer, and then 50 parts by mass of a plasticizer was added until uniform. The mixture was handled and mixed to obtain a vinyl chloride resin composition. This resin composition was melt-kneaded at 160 to 166° C. for 4 minutes using a 5×12 inch twin roll to prepare a roll sheet. Subsequently, press molding was performed at 162 to 168° C. for 10 minutes to prepare a press sheet with a thickness of about 1 mm.

<Evaluation of physical properties of vinyl chloride resin molding>
(4) Tensile properties: 100% modulus, breaking strength and breaking elongation of the press sheet were measured according to JISK-6723 (1995). The smaller the 100% modulus value, the better the flexibility, and the breaking strength and breaking elongation are indicators of the practical strength of the material, and generally, the larger the value, the more practical strength. can say excellent.

(5) Cold resistance: Measured in accordance with JISK-6773 (1999) using a Crashberg tester. The lower the softening temperature (°C), the better the cold resistance. The flexible temperature referred to here refers to the temperature at which the torsional rigidity (3.17×10 ³ kg/cm ² ) described in JIS is exhibited in the above measurement.
<Evaluation of softening temperature>
[I]: -30°C or less [II]: -25°C or less -30°C or more [III]: -25°C or more

(6) Heat resistance: Based on evaluation of volatility loss and sheet coloration.
a) Volatile loss: The change in mass of the roll sheet was measured after heating the roll sheet at 170°C for 60 minutes and 120 minutes in a gear oven, and the mass reduction rate (% by mass) was calculated from the following formula.
The smaller the numerical value, the higher the heat resistance.
Volatile loss (%) = ((mass before test - mass after test) / mass before test) x 100
<Evaluation of Volatile Loss (170°C, 120 minutes)>
[I]: Less than 13% [II]: 13% or more and less than 15% [III]: 15% or more b) Sheet coloring: In a gear oven, the degree of coloring after heating the roll sheet at 170 ° C. for 30 minutes and 60 minutes The strength of the strength was visually evaluated in three stages.
<Evaluation of sheet coloring>
[I]: ○ No coloring [II]: △ Slightly coloring [III]: × Coloring

(7) Performance evaluation of vinyl chloride resin molded product As a performance evaluation of the vinyl chloride resin molded product, the evaluation of the softening temperature, the evaluation of the volatile loss (170 ° C., 120 minutes), and the evaluation of the sheet coloring are as follows. If [III] is 1 or more, it is evaluated as unsuitable, if [II] is 1 or less (other evaluations are [I]), it is evaluated as good, and if all evaluations are [I], it is evaluated as particularly good.

(8) Biomass degree To measure the biomass degree of diester, the sample to be measured is burned to generate carbon dioxide, and the carbon dioxide purified in a vacuum line is reduced with hydrogen using iron as a catalyst to produce graphite. Then, this graphite is mounted on a tandem accelerator-based ¹⁴ C-AMS dedicated device (manufactured by NEC) to count ¹⁴ C, the concentration of ¹³ C ( ¹³ C/ ¹² C), and the concentration of ¹⁴ C ( ¹⁴ C/ ¹² C) is measured and from this measurement the ratio of ¹⁴ C concentration of sample carbon to standard modern carbon is calculated. In this measurement, oxalic acid (HOxII) provided by the US National Institute of Standards (NIST) was used as a standard sample.

[Production Example 1]
4-Cyclohexene-1,2-dicarboxylic anhydride (2.00 mol), n-octanol (4.80 mol), And 0.4 g of tetraisopropyl titanate (manufactured by Nippon Soda Co., Ltd.) was added as an esterification catalyst, and an esterification reaction was carried out at a reaction temperature of 200°C. The reaction was carried out until the acid value of the reaction solution reached 0.2 mgKOH/g while removing the generated water out of the system by refluxing the alcohol under reduced pressure. After completion of the reaction, unreacted alcohol is distilled out of the system under reduced pressure, followed by neutralization with a 2% NaOH aqueous solution, washing with water, and dehydration in a conventional manner to obtain the 4-cyclohexene-1,2-dicarboxylic acid dicarboxylic acid according to the present invention. 682.5 g of n-octyl (hereinafter referred to as "ester 1") was obtained.
The resulting ester 1 had an acid value of 0.01 mgKOH/g, a hue (Hazen) of 20, and a degree of biomass of 66.7%.

[Production Example 2]
In the same manner as in Production Example 1, except that n-octanol (3.84 mol), n-dodecanol (0.77 mol), and n-tetradecanol (0.19 mol) were added instead of n-octanol. As a result, 702.0 g of a 4-cyclohexene-1,2-dicarboxylic acid diester mixture according to the present invention (hereinafter referred to as "ester 2") was obtained.
Each component was quantified by GC analysis using DOP as a standard substance, and di-n-octyl 4-cyclohexene-1,2-dicarboxylate was 64.0 mol%, and 4-cyclohexene-1,2-dicarboxylic acid = n-octyl = 25.0 mol % of n-dodecyl, 7.0 mol % of 4-cyclohexene-1,2-dicarboxylic acid = n-octyl = n-tetradecyl, and 2.0 mol % of di-n-dodecyl 4-cyclohexene-1,2-dicarboxylate. 4 mol %, 4-cyclohexene-1,2-dicarboxylic acid=n-dodecyl=n-tetradecyl was 1.4 mol %, and di-n-tetradecyl 4-cyclohexene-1,2-dicarboxylic acid was 0.2 mol %.
The resulting ester 2 had an acid value of 0.01 mgKOH/g, a hue (Hazen) of 13, and a degree of biomass of 69.0%.

[Production Example 3]
In the same manner as in Production Example 1, except that n-octanol (2.40 mol), n-dodecanol (1.87 mol), and n-tetradecanol (0.53 mol) were added instead of n-octanol. As a result, 778.0 g of a 4-cyclohexene-1,2-dicarboxylic acid diester mixture according to the present invention (hereinafter referred to as "ester 3") was obtained.
Each component was quantified by GC analysis using DOP as a standard substance. 39.0 mol % of n-dodecyl, 11.0 mol % of 4-cyclohexene-1,2-dicarboxylic acid=n-octyl=n-tetradecyl, and 15.0 mol % of di-n-dodecyl 4-cyclohexene-1,2-dicarboxylate. 0 mol %, 8.7 mol % of 4-cyclohexene-1,2-dicarboxylic acid=n-dodecyl=n-tetradecyl, and 1.3 mol % of di-n-tetradecyl 4-cyclohexene-1,2-dicarboxylic acid.
The resulting ester 3 had an acid value of 0.01 mgKOH/g, a hue (Hazen) of 15, and a degree of biomass of 71.9%.

[Production Example 4]
In the same manner as in Production Example 1, except that n-octanol (0.96 mol), n-dodecanol (2.98 mol), and n-tetradecanol (0.86 mol) were added instead of n-octanol. As a result, 871.0 g of a 4-cyclohexene-1,2-dicarboxylic acid diester mixture according to the present invention (hereinafter referred to as "ester 4") was obtained.
Each component was quantified by GC analysis using DOP as a standard substance, and 4-cyclohexene-1,2-dicarboxylic acid di-n-octyl was 4.0 mol%, and 4-cyclohexene-1,2-dicarboxylic acid = n-octyl = 25.0 mol % of n-dodecyl, 7.2 mol % of 4-cyclohexene-1,2-dicarboxylic acid=n-octyl=n-tetradecyl, and 38.2 mol % of di-n-dodecyl 4-cyclohexene-1,2-dicarboxylate. 0 mol %, 22.0 mol % of 4-cyclohexene-1,2-dicarboxylic acid=n-dodecyl=n-tetradecyl, and 3.2 mol % of di-n-tetradecyl 4-cyclohexene-1,2-dicarboxylic acid.
The resulting ester 4 had an acid value of 0.01 mgKOH/g, a hue (Hazen) of 11, and a degree of biomass of 74.4%.

[Example 1]
As the biomass plasticizer of the present invention, biomass plasticizer 1 was obtained by mixing 95% by mass of ester 1 obtained in Production Example 1 and 5% by mass of epoxidized soybean oil. The biomass degree of the biomass plasticizer 1 was 68.3%.
A vinyl chloride resin composition was produced using the biomass plasticizer 1 as described above in "(2) Production of vinyl chloride press sheet". Subsequently, a vinyl chloride sheet was produced from the obtained vinyl chloride resin composition, and a tensile test, a cold resistance test and a heat resistance test were carried out. The obtained results are summarized in Table 1.

[Example 2]
As the biomass plasticizer of the present invention, a biomass plasticizer 2 was obtained by mixing 80% by mass of the ester 1 obtained in Production Example 1 and 20% by mass of epoxidized soybean oil. The biomass degree of the biomass plasticizer 2 was 73.2%.
A vinyl chloride resin composition and a vinyl chloride sheet were prepared in the same manner as in Example 1, except that biomass plasticizer 2 was used instead of biomass plasticizer 1, and tensile tests, cold resistance tests, and heat resistance tests were performed. . The obtained results are summarized in Table 1.

[Example 3]
As the biomass plasticizer of the present invention, biomass plasticizer 3 was obtained by mixing 50% by mass of ester 1 obtained in Production Example 1 and 50% by mass of epoxidized soybean oil. The biomass degree of the biomass plasticizer 3 was 83.2%.
A vinyl chloride resin composition and a vinyl chloride sheet were prepared in the same manner as in Example 1, except that biomass plasticizer 3 was used instead of biomass plasticizer 1, and tensile tests, cold resistance tests, and heat resistance tests were performed. . The obtained results are summarized in Table 1.

[Example 4]
As the biomass plasticizer of the present invention, a biomass plasticizer 4 was obtained by mixing 80% by mass of the ester 2 obtained in Production Example 2 and 20% by mass of epoxidized soybean oil. The biomass degree of the biomass plasticizer 4 was 75.0%.
A vinyl chloride resin composition and a vinyl chloride sheet were prepared in the same manner as in Example 1, except that biomass plasticizer 4 was used instead of biomass plasticizer 1, and tensile tests, cold resistance tests, and heat resistance tests were performed. . The obtained results are summarized in Table 1.

[Example 5]
As the biomass plasticizer of the present invention, biomass plasticizer 5 was obtained by mixing 50% by mass of ester 2 obtained in Production Example 2 and 50% by mass of epoxidized soybean oil. The biomass degree of the biomass plasticizer 5 was 84.3%.
A vinyl chloride resin composition and a vinyl chloride sheet were prepared in the same manner as in Example 1 except that biomass plasticizer 5 was used instead of biomass plasticizer 1, and tensile tests, cold resistance tests, and heat resistance tests were performed. . The obtained results are summarized in Table 1.

[Example 6]
As the biomass plasticizer of the present invention, a biomass plasticizer 6 was obtained by mixing 80% by mass of the ester 3 obtained in Production Example 3 and 20% by mass of epoxidized soybean oil. The biomass degree of the biomass plasticizer 6 was 77.3%.
A vinyl chloride resin composition and a vinyl chloride sheet were prepared in the same manner as in Example 1, except that biomass plasticizer 6 was used instead of biomass plasticizer 1, and tensile tests, cold resistance tests, and heat resistance tests were performed. . The obtained results are summarized in Table 1.

[Example 7]
As the biomass plasticizer of the present invention, biomass plasticizer 7 was obtained by mixing 50% by mass of ester 3 obtained in Production Example 3 and 50% by mass of epoxidized soybean oil. The biomass degree of the biomass plasticizer 7 was 85.7%.
A vinyl chloride resin composition and a vinyl chloride sheet were prepared in the same manner as in Example 1, except that biomass plasticizer 7 was used instead of biomass plasticizer 1, and tensile tests, cold resistance tests, and heat resistance tests were performed. . The obtained results are summarized in Table 1.

[Comparative Example 1]
As a plasticizer, a plasticizer 8 was obtained by mixing 20% by mass of the ester 1 obtained in Production Example 1 and 80% by mass of epoxidized soybean oil. The biomass degree of plasticizer 8 was 93.2%.
A vinyl chloride resin composition was prepared using the plasticizer 8 as described in "(2) Production of vinyl chloride press sheet" above. Subsequently, a vinyl chloride sheet was produced from the obtained vinyl chloride resin composition, and a tensile test, a cold resistance test and a heat resistance test were carried out. The obtained results are summarized in Table 1.

[Comparative Example 2]
As a plasticizer, a plasticizer 9 was obtained by mixing 20% by mass of the ester 2 obtained in Production Example 2 and 80% by mass of epoxidized soybean oil. The biomass degree of plasticizer 9 was 93.6%.
A vinyl chloride resin composition and a vinyl chloride sheet were prepared in the same manner as in Comparative Example 1 except that plasticizer 9 was used instead of plasticizer 8, and tensile test, cold resistance test and heat resistance test were performed. The obtained results are summarized in Table 1.

[Comparative Example 3]
As a plasticizer, a plasticizer 10 was obtained by mixing 20% by mass of the ester 3 obtained in Production Example 3 and 80% by mass of epoxidized soybean oil. The biomass degree of plasticizer 10 was 94.2%.
A vinyl chloride resin composition and a vinyl chloride sheet were prepared in the same manner as in Comparative Example 1 except that plasticizer 10 was used instead of plasticizer 8, and tensile test, cold resistance test and heat resistance test were performed. The obtained results are summarized in Table 1.

[Comparative Example 4]
A vinyl chloride resin composition and a vinyl chloride sheet were prepared in the same manner as in Comparative Example 1 except that the ester 4 obtained in Production Example 4 was used as the plasticizer 11 instead of the plasticizer 8, and the sheet was stretched. A test, a cold resistance test and a heat resistance test were carried out. The obtained results are summarized in Table 1.

[Comparative Example 5]
A vinyl chloride resin composition and a vinyl chloride sheet were prepared in the same manner as in Example 1 except that DOP was used as a plasticizer instead of plasticizer 8, and tensile test, cold resistance test and heat resistance test were performed. The obtained results are summarized in Table 2.

[Comparative Example 6]
A vinyl chloride resin composition and a vinyl chloride sheet were prepared in the same manner as in Example 1 except that DINP was used as a plasticizer instead of plasticizer 8, and tensile tests, cold resistance tests and heat resistance tests were performed. The obtained results are summarized in Table 2.

[Comparative Example 7]
A vinyl chloride resin composition and a vinyl chloride sheet were prepared in the same manner as in Example 1 except that DOTH was used as a plasticizer instead of plasticizer 8, and tensile tests, cold resistance tests and heat resistance tests were performed. The obtained results are summarized in Table 2.

[Comparative Example 8]
A vinyl chloride resin composition and a vinyl chloride sheet were prepared in the same manner as in Example 1 except that ester 1 was used as a plasticizer instead of plasticizer 8, and tensile tests, cold resistance tests, and heat resistance tests were performed. . The obtained results are summarized in Table 2.

[Comparative Example 9]
A vinyl chloride resin composition and a vinyl chloride sheet were prepared in the same manner as in Example 1 except that ester 2 was used as a plasticizer instead of plasticizer 8, and tensile tests, cold resistance tests, and heat resistance tests were performed. . The obtained results are summarized in Table 2.

[Comparative Example 10]
A vinyl chloride resin composition and a vinyl chloride sheet were prepared in the same manner as in Example 1 except that ester 3 was used as a plasticizer instead of plasticizer 8, and tensile tests, cold resistance tests, and heat resistance tests were performed. . The obtained results are summarized in Table 2.

[Comparative Example 11]
A vinyl chloride resin composition and a vinyl chloride sheet were prepared in the same manner as in Example 1 except that epoxidized soybean oil was used as a plasticizer instead of plasticizer 8, and tensile test, cold resistance test and heat resistance test were performed. did. The obtained results are summarized in Table 2.

From Table 1, the biomass plasticizer for vinyl chloride resin according to the present invention described in Examples 1 to 7 has a low softening temperature of -27 ° C. or less and a volatile loss (170 ° C., 120 minutes) of 12.8%. It can be seen that the sheet is not colored, and the biomass degree is 68.3% or more.

By replacing the composition of the plasticizer for vinyl chloride resins with the plant-derived biomass plasticizer for vinyl chloride resins according to the present invention from a state where all plasticizers for vinyl chloride resins are petroleum-derived plasticizers, petroleum resources In addition to reducing the amount used, the environmental load can be reduced by suppressing the amount of carbon dioxide emissions during the production of plasticizers for vinyl chloride resins.
Since the biomass plasticizer for vinyl chloride resin according to the present invention has excellent compatibility with vinyl chloride resin, it has excellent plasticization efficiency and flexibility, can impart excellent heat resistance and cold resistance, and has a specific It can be suitably used as a biomass plasticizer for vinyl chloride resins having a biomass degree.
The vinyl chloride resin composition and the vinyl chloride resin molding characterized by containing the biomass plasticizer for vinyl chloride resin according to the present invention are excellent in cold resistance and heat resistance and have good flexibility. It can be used as a plasticizer for vinyl chloride resins, and a molded product obtained from a vinyl chloride resin composition containing the plasticizer is used for electric wire coating applications that require high cold resistance, heat resistance, and flexibility. and automotive parts, general film sheets (laminates, packaging, vehicles, miscellaneous goods, etc.), agricultural films, leather, compounds, flooring, wallpaper, footwear, sealing materials, textiles, hoses It is very useful for applications, gasket applications, building material applications, paint applications, adhesive applications, paste applications, and medical applications.

Claims (6)

(A) Component:
General formula (1)

[In the formula, R ¹ and R ² are the same or different and each represent a biomass-derived linear alkyl group having 8 to 14 carbon atoms. ]
One or a mixture of two or more 4-cyclohexene-1,2-dicarboxylic acid diesters represented by and component (B): a biomass plasticizer for vinyl chloride resins containing epoxidized vegetable oil,
Vinyl chloride, wherein the component (A) has a biomass degree of 50 to 100%, and the mass ratio of the component (A) and the component (B) is 50 to 99% by mass: 1 to 50% by mass. Biomass plasticizer for system resins. The biomass plasticizer for vinyl chloride resins according to claim 1, wherein the component (A) is di-n-octyl 4-cyclohexene-1,2-dicarboxylate. Component (A) is (a) di-n-octyl 4-cyclohexene-1,2-dicarboxylate, (b) 4-cyclohexene-1,2-dicarboxylic acid = n-octyl = n-dodecyl, and (c) 4 -cyclohexene-1,2-dicarboxylic acid = n-octyl = n-tetradecyl, (d) di-n-dodecyl 4-cyclohexene-1,2-dicarboxylic acid, (e) 4-cyclohexene-1,2-dicarboxylic acid = 2. The biomass plasticizer for vinyl chloride resins according to claim 1, wherein n-dodecyl=n-tetradecyl and (f) di-n-tetradecyl 4-cyclohexene-1,2-dicarboxylate. (A) component: the total of (a) to (f) is 100 mol%, and
(a): (b): (c): (d): (e): (f) = 20.0 to 67.2 mol%: 19.8 to 40.7 mol%: 5.7 to 11.8 mol% : 1.9-15.8 mol%: 1.1-9.2 mol%, : 0.1-1.4 mol%, the biomass plasticizer for vinyl chloride resin according to claim 3. A vinyl chloride resin composition comprising a vinyl chloride resin and the biomass plasticizer for vinyl chloride resin according to any one of claims 1 to 4. A molded article obtained from the vinyl chloride resin composition according to claim 5 .