JP7066107B2 - Polyvinyl chloride resin composition - Google Patents

Description

The present invention relates to a polyvinyl chloride resin composition having excellent appearance, antifouling property and thermal stability.

Polyvinyl chloride resin is used in a wide range of fields as a general-purpose resin. In particular, antifouling properties are required for applications such as wallpaper, decorative films, and resin sashes that are visible to human eyes. Further, the polyvinyl chloride resin is required to have thermal stability because hydrogen chloride is desorbed due to the heat history during the molding process and corrodes the processing machine.

Patent Document 1 discloses a method of imparting antifouling property by adding organopolysiloxane to a polyvinyl chloride resin. However, since the polyvinyl chloride resin and the organopolysiloxane are incompatible with each other, there is a drawback that the organopolysiloxane bleeds out from the surface of the molded product.

In Patent Document 2, a polyvinyl chloride resin is made of poly by adding a copolymer of an organopolysiloxane group-containing monomer, a methyl methacrylate monomer, and a -2-ethylhexyl acrylate monomer. A method for imparting antifouling property to a vinyl chloride resin is disclosed. This improves the compatibility between the polyvinyl chloride resin and the copolymer.

Japanese Unexamined Patent Publication No. 63-6044 Japanese Unexamined Patent Publication No. 9-143326

However, since the copolymer described in Patent Document 2 is a copolymer in which an organopolysiloxane group-containing monomer and other monomers are randomly arranged, it has poor surface transferability and antifouling property. It has turned out to be inadequate.

An object of the present invention is to provide a polyvinyl chloride resin composition having excellent appearance, antifouling property and thermal stability.

（式（１）において、ｎは５～５００の整数を表す。）
The present invention is as follows.
(1) A polyvinyl chloride resin composition comprising 0.5 to 10 parts by mass of the following component (B) with respect to 100 parts by mass of the following component (A).

(A) Polyvinyl chloride resin

(B) An organopolysiloxane group-containing block copolymer.
(I) A segment containing an organopolysiloxane group and (II) a segment not containing an organopolysiloxane group are contained in a mass ratio ((I) / (II)) of 60/40 to 80/20.
(I) The segment containing the organopolysiloxane group is (b-1) an organopolysiloxane group-containing monomer represented by the following formula (1) and (b-2) a single amount of (meth) acrylic acid alkyl ester. The body is polymerized at a mass ratio ((b-1) / (b-2)) of 40/60 to 60/40.
(II) An organopolysiloxane group-containing block copolymer, wherein the segment containing no organopolysiloxane group is formed by polymerizing a (b-3) (meth) acrylic acid alkyl ester monomer.

(In equation (1), n represents an integer of 5 to 500.)

(2) The polyvinyl chloride resin composition of (1), which contains 5 to 150 parts by mass of (C) a plasticizer with respect to 100 parts by mass of the component (A).

(3) The polyvinyl chloride resin composition according to (1) or (2), which contains 50 to 150 parts by mass of the filler (D) with respect to 100 parts by mass of the component (A).

According to the present invention, it is possible to provide a polyvinyl chloride resin composition having excellent appearance, antifouling property and thermal stability.

Hereinafter, the present invention will be described in more detail.
<(A) Polyvinyl chloride resin>
Examples of the polyvinyl chloride resin include homopolymers of vinyl chloride monomers and copolymers with other monomers. The average degree of polymerization of the polyvinyl chloride resin is preferably in the range of 500 to 5,000.
By setting the average degree of polymerization of the polyvinyl chloride resin to 500 or more, the strength tends to be improved. The processability tends to be improved by setting the average degree of polymerization of the polyvinyl chloride resin to 5,000 or less.

The method for producing the polyvinyl chloride resin is not particularly limited, and can be obtained by a known bulk polymerization method, suspension polymerization method, or emulsification polymerization method.

<(B) Organopolysiloxane group-containing block copolymer>
The block copolymer containing an organopolysiloxane group has (I) a segment containing an organopolysiloxane group and (II) a segment containing no organopolysiloxane group. Each of the segments (I) and (II) is bonded with a linear alkylene group or a branched alkylene group having 1 to 18 carbon atoms derived from the polymer peroxide.

<(I) Segment containing organopolysiloxane group>
The segment containing the organopolysiloxane group is polymerized with the organopolysiloxane group-containing monomer represented by the formula (b-1) (1) and the (meth) acrylic acid alkyl ester monomer (b-2). It becomes.

In the formula (1), n represents an integer of 5 to 500. From the viewpoint of the present invention, n is preferably 50 or more, preferably 300 or less, and particularly preferably 200 or less.

Examples of the (meth) acrylic acid alkyl ester monomer include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, -n-propyl (meth) acrylic acid, isopropyl (meth) acrylic acid, and (meth) acrylic. Acid-n-butyl, (meth) acrylic acid isobutyl, (meth) acrylic acid-tert-butyl, (meth) acrylic acid-n-pentyl, (meth) acrylic acid-n-hexyl, (meth) acrylic acid-n -Heptyl, (meth) acrylic acid-n-octyl, (meth) acrylic acid-2-ethylhexyl and the like can be mentioned. Further, as the (meth) acrylic acid alkyl ester monomer, one kind may be used, or two or more kinds may be used.

<(II) Segment containing no organopolysiloxane group>
The segment containing no organopolysiloxane group is formed by polymerizing the (b-3) (meth) acrylic acid ester monomer.

Examples of the (meth) acrylic acid alkyl ester monomer include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, -n-propyl (meth) acrylic acid, isopropyl (meth) acrylic acid, and (meth) acrylic. Acid-n-butyl, (meth) acrylic acid isobutyl, (meth) acrylic acid-tert-butyl, (meth) acrylic acid-n-pentyl, (meth) acrylic acid-n-hexyl, (meth) acrylic acid-n -Heptyl, (meth) acrylic acid-n-octyl, (meth) acrylic acid-2-ethylhexyl and the like can be mentioned. Further, as the (meth) acrylic acid alkyl ester monomer, one kind may be used, or two or more kinds may be used.

In the block copolymer containing an organopolysiloxane group, the composition ratio ((I) / (II)) of the segment containing (I) an organopolysiloxane group and the segment not containing (II) an organopolysiloxane group is a mass ratio. It is set to 60/40 to 80/20. (I) If the mass ratio of the segment containing the organopolysiloxane group is lower than 60, the antifouling property tends to decrease, so the value is 60 or more. Further, if the ratio of the segment containing (I) an organopolysiloxane group exceeds 80, the appearance tends to deteriorate, so the ratio is 80 or less.

(I) In the segment containing an organopolysiloxane group, the composition ratio ((b-1) / (b-2)) of the organopolysiloxane group-containing monomer and the (meth) acrylic acid alkyl ester monomer is , 40/60 to 60/40 is preferable in terms of mass ratio. When the ratio of the organopolysiloxane group-containing monomer is less than 40, the antifouling property is lowered. When the ratio of the organopolysiloxane group-containing monomer exceeds 60, the appearance is deteriorated.

(B-1) The organopolysiloxane group-containing block copolymer can be produced by a production method comprising the following first and second steps.
The first step is a step of polymerizing a monomer forming a segment containing an organopolysiloxane group using a polymer peroxide as a polymerization initiator to obtain a peroxy bond-containing polymer.
The second step is a step of polymerizing a monomer forming a segment containing no organopolysiloxane group using the obtained peroxy bond-containing polymer as a polymerization initiator.

A polymer peroxide is a compound having two or more peroxy bonds in one molecule. As the polymer peroxide, for example, one represented by the following formula can be used.

（式中、ｍは２～２０の整数を表す。）

(In the formula, m represents an integer of 2 to 20.)

（式中、ｌは２～２０の整数を表す。）

(In the formula, l represents an integer of 2 to 20.)

The polymer peroxides may be used alone or in combination of two or more.

The organopolysiloxane group-containing block copolymer can be obtained by a solution polymerization method, a bulk polymerization method, a suspension polymerization method, or an emulsion polymerization method using the polymer peroxide.

The obtained organopolysiloxane group-containing block copolymer can be used as an emulsion by dissolving or dispersing it in the solvent shown below, or by adding a surfactant or the like and dispersing it in water. It can also be used in the form of fine powder.

The polymerization solvent and the diluting solvent are not particularly limited as long as they are solvents that can dissolve or disperse the organopolysiloxane group-containing block copolymer, but for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate. , Methylcellosorbate acetate, tetrahydrofuran, dimethylformamide, dimethylacetamide, toluene, ethylbenzene, xylene, hexane, heptane, isoparaffin solvent, methyl alcohol, ethyl alcohol, propyl alcohol and the like. These solvents may be used alone or in combination of two or more.

The amount of the organopolysiloxane group-containing block copolymer is preferably 0.5 to 10 parts by mass, more preferably 1 to 6 parts by mass with respect to 100 parts by mass of the polyvinyl chloride resin. If the amount of the organopolysiloxane group-containing block copolymer is less than 0.5 parts by mass, the antifouling property tends to decrease. When the amount of the organopolysiloxane group-containing block copolymer exceeds 10 parts by mass, the appearance tends to deteriorate.

<(C) Plasticizer>
The plasticizer used in the present invention is not particularly limited, and can be arbitrarily selected and used from those conventionally used for polyvinyl chloride resin. Examples of such a plasticizer include alkyl esters of aromatic polybasic acids such as dibutyl phthalate, dioctyl phthalate, diisodecyl phthalate, diisononyl phthalate, diun decyl phthalate, trioctyl limerate, triiso octyl limelite, and pyromeritate. Alcohol esters of aliphatic polybasic acids such as dibutyl adipate, dioctyl adipate, diisononyl adipate, dibutyl azelate, dioctyl azelate, diisononyl azelate; phosphate esters such as tricresyl phosphate; adipic acid, azelaic acid, sebacic acid , A polycondensate of a polyvalent carboxylic acid such as phthalic acid and a polyhydric alcohol such as ethylene glycol, 1,2-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol and 1,4-butylene glycol. Ester-based plasticizers such as those whose ends are sealed with monohydric alcohol or monovalent carboxylic acid; epoxidized plasticizers such as epoxidized soybean oil, epoxidized flaxseed oil, and epoxidized toll oil fatty acid 2-ethylhexyl; chlorination Examples include paraffin.

Each of these plasticizers may be used alone or in combination of two or more, and among these, phthalate-based plasticizers such as dioctylphthalate and diisononylphthalate have less bleeding. Is preferable. The amount of the plasticizer to be blended is not particularly limited as long as the plasticizing effect is exhibited, the elasticity and elongation of the obtained molded product are sufficient, and the hardness is not too high. Mechanical properties tend to decline. Therefore, it is preferably 5 to 150 parts by mass, more preferably 10 to 100 parts by mass, still more preferably 10 to 80 parts by mass with respect to 100 parts by mass of the polyvinyl chloride resin.

<(D) Filler>
Examples of the filler used in the present invention include calcium carbonate, talc, kaolin clay, mica, synthetic silicic acid, silica stone powder, barium sulfate and the like. Of these, calcium carbonate is more preferable. The particle size, powder properties, production method and the like of calcium carbonate are not particularly limited, but the particle size is preferably 0.5 μm to 10 μm in consideration of dispersibility with respect to the polyvinyl chloride resin. These fillers are preferably 50 to 150 parts by mass with respect to 100 parts by mass of the polyvinyl chloride resin, and more preferably 100 to 140 parts by mass in consideration of flame retardancy.

<Other additives>
To the polyvinyl chloride resin composition of the present invention, other additions such as a foaming agent, a stabilizer, an antioxidant, a processing aid, a flame retardant, an ultraviolet absorber, and a colorant are added as long as the effects of the present invention are not impaired. Agents can be added.

The polyvinyl chloride resin composition of the present invention is excellent in antifouling property. Therefore, it can be used as a material for wallpaper, decorative films, and resin sashes.

Hereinafter, specific examples of the present invention will be described.
<Block copolymer containing organopolysiloxane group>
(Manufacturing Examples 1-5, 7-9)
A 500 ml four-necked flask equipped with a stirrer, a thermometer, and a condenser is charged with a monomer forming a segment containing the solvent, the initiator, and the organopolysiloxane group shown in Tables 1 and 2, and is charged at 70 ° C. for 3 hours. A polymerization reaction was carried out. Subsequently, the monomers forming the segments containing no organopolysiloxane group shown in Table 1 were charged and polymerized at 80 ° C. for 3 hours to obtain an organopolysiloxane group-containing block copolymer.

<Random copolymer containing organopolysiloxane group>
(Manufacturing Example 6)
A 500 ml four-necked flask equipped with a stirrer, a thermometer, and a condenser was charged with the solvent, initiator, and monomer shown in Table 2, and the polymerization reaction was carried out at 70 ° C. for 6 hours. I got a coalescence.

<Polyvinyl chloride resin composition>
(Examples 1 to 5, Comparative Examples 1 to 6)
Each component was mixed in each composition shown in Tables 3 and 4 at 25 ° C. for 3 minutes with a stirrer. Subsequently, this mixture was applied to the wallpaper base paper and heated at 220 ° C. for 5 minutes in a gear oven to obtain a test piece.

The evaluation method of each performance is as follows.
<Appearance>
The surface of the test piece was visually observed to evaluate the presence or absence of appearance defects such as bleed-out.

<Anti-fouling (water-based stain)>
With a water-based felt-tip pen (Pentel water-based felt-tip pen), draw 5 lines on the test piece at 2 mm intervals and let it stand for 24 hours, then wipe off the dirt with a cotton cloth soaked in water, and visually observe the remaining state of the dirt. Scored according to the following criteria.

5: No stains remain 4: Almost no stains remain 3: Some stains remain 2: Some stains remain 1: Some stains remain strongly

<Anti-fouling (oil-based stain)>
With an oil-based felt-tip pen (Zebra's McKee Care extra-fine), draw 5 lines on the test piece at 2 mm intervals, let stand for 24 hours, wipe off the dirt with a cotton cloth soaked in ethanol, and visually observe the remaining state of the dirt. , Scored according to the following criteria.
In addition, 4 points or more were passed for both water-based stains and oil-based stains.

5: No stains remain 4: Almost no stains remain 3: Some stains remain 2: Some stains remain 1: Some stains remain strongly

<Thermal stability>
Since the color changes due to the formation of polyene due to the desorption of hydrogen chloride in the polyvinyl chloride resin, the degree of discoloration was used as an index of thermal stability. Leave the white test piece in a gear oven set at 180 ° C for 1 hour (assuming long-term retention due to a malfunction of the processing machine), and visually check the discoloration (white, brown, dark brown, black). Observed. In addition, up to brown was accepted.

ＰＶ： 日油製ｔｅｒｔ－ブチルペルオキシピバレート

ＦＭ０７２１：ＪＮＣ製サイラプレーンＦＭ０７２１
（式（１）の構造：ｎ＝６４）
ＦＭ０７２５：ＪＮＣ製サイラプレーンＦＭ０７２５
（式（１）の構造：ｎ＝１３１）
ＦＭ０７１１：ＪＮＣ製サイラプレーンＦＭ０７１１
（式（１）の構造：ｎ＝１０）
ＭＭＡ： メタクリル酸メチル
ＢＭＡ： メタクリル酸－ｎ－ブチル
The details of the materials shown in Tables 1 and 2 are as follows.
MEK: Methyl ethyl ketone PPO:

PV: NOF tert-butylperoxypivalate

FM0721: JNC silaplane FM0721
(Structure of equation (1): n = 64)
FM0725: JNC Silaplane FM0725
(Structure of equation (1): n = 131)
FM0711: JNC silaplane FM0711
(Structure of equation (1): n = 10)
MMA: Methyl Methacrylate BMA: -n-Butyl Methacrylate

The details of the materials shown in Tables 3 and 4 are as follows.

Polyvinyl chloride resin: Kaneka PSL-675
Plasticizer: Daihachi Chemical Industry Diisononyl Phthalate Calcium Carbonate: Shiraishi Calcium Whiten SB Blue Foaming Agent: Eiwa Kasei Kogyo Vinihole AC # 3C-K2
Stabilizer: ADEKA FL-103N

As is clear from the results in Tables 1 and 3, all of Examples 1 to 4 were excellent in appearance, antifouling property, and thermal stability.

On the other hand, as can be seen from Tables 1, 2 and 4, the balance of these performances was insufficient in Comparative Examples 1 to 6.

Specifically, Comparative Example 1 was inferior in antifouling property because the amount of the organopolysiloxane group-containing block copolymer was too small.
Comparative Example 2 was inferior in appearance and thermal stability due to an excess of the organopolysiloxane group-containing block copolymer.

In Comparative Example 3, since the organopolysiloxane group-containing copolymer was a random copolymer, it was inferior in antifouling property and thermal stability.
In Comparative Example 4, the antifouling property was inferior because the ratio of the segment containing the organopolysiloxane group to the segment not containing the organopolysiloxane group was not suitable.

Comparative Example 5 was inferior in appearance due to the excess of the organopolysiloxane group-containing monomer.
Comparative Example 6 was inferior in antifouling property because the amount of the organopolysiloxane group-containing monomer was too small.

Hereinafter, suitable compounding examples of the polyvinyl chloride resin composition of the present invention will be described.
However, in Formulation Examples 1 to 6, PSL-675 manufactured by Kaneka is used as the polyvinyl chloride resin, Production Example 1 is used as the organopolysiloxane group-containing block copolymer, and Daihachi Chemical Industry Co., Ltd. is used as the plasticizer. Diisononyl phthalate manufactured by Shiraishi Calcium is used as calcium carbonate, Vinihole AC # 3C-K2 manufactured by Eiwa Kasei Kogyo is used as a foaming agent, and FL-103N manufactured by Adeca is used as a stabilizer. used.

<Combination example 1>
Polyvinyl chloride resin: 100 parts by mass Organopolysiloxane group-containing block copolymer: 2 parts by mass Plastic agent: 50 parts by mass Calcium carbonate: 100 parts by mass Foaming agent: 3 parts by mass Stabilizer: 5 parts by mass Pentaerythritol tetrakis [3] -(3,5-di-tert-butyl-4-hydroxyphenyl) propionate]:
0.1 part by mass

<Combination example 2>
Polyvinyl chloride resin: 100 parts by mass Organopolysiloxane group-containing block copolymer: 2 parts by mass Plasticizer: 50 parts by mass Calcium carbonate: 100 parts by mass Foaming agent: 3 parts by mass Dibutyltin distearate: 3 parts by mass

<Combination example 3>
Polyvinyl chloride resin: 100 parts by mass Organopolysiloxane group-containing block copolymer: 2 parts by mass Epoxidized soybean oil: 50 parts by mass Calcium carbonate: 100 parts by mass Foaming agent: 3 parts by mass Stabilizer: 5 parts by mass

<Combination example 4>
Polyvinyl chloride resin: 100 parts by mass Organopolysiloxane group-containing block copolymer: 2 parts by mass Plasticizer: 50 parts by mass Calcium carbonate: 100 parts by mass Foaming agent: 3 parts by mass Zincstearate: 1 part by mass Triphenylphosphine: 1 part by mass

<Formulation Example 5>
Polyvinyl chloride resin: 100 parts by mass Organopolysiloxane group-containing block copolymer: 2 parts by mass Plastic agent: 50 parts by mass Calcium carbonate: 100 parts by mass Foaming agent: 3 parts by mass Zincesterate: 1 part by mass of dipentaerythritol Adipic acid ester: 1 part by mass

<Formulation Example 6>
Polyvinyl chloride resin: 100 parts by mass Organopolysiloxane group-containing block copolymer: 2 parts by mass Plasticizer: 50 parts by mass Calcium carbonate: 100 parts by mass Foaming agent: 3 parts by mass Zincstearate: 1 part by mass Dibenzoylmethane: 1 part by mass

The polyvinyl chloride resin compositions obtained in Formulation Examples 1 to 6 were all excellent in appearance, stain resistance, and thermal stability.

Claims (3)

A polyvinyl chloride resin composition comprising 0.5 to 10 parts by mass of the following component (B) with respect to 100 parts by mass of the following component (A).

(A) Polyvinyl chloride resin

(B) An organopolysiloxane group-containing block copolymer.
(I) A segment containing an organopolysiloxane group and (II) a segment not containing an organopolysiloxane group are contained in a mass ratio ((I) / (II)) of 60/40 to 80/20.
(I) The segment containing the organopolysiloxane group is (b-1) an organopolysiloxane group-containing monomer represented by the following formula (1) and a single amount of (b-2) (meth) acrylic acid alkyl ester. The body is polymerized at a mass ratio ((b-1) / (b-2)) of 40/60 to 60/40.
(II) An organopolysiloxane group-containing block copolymer, wherein the segment containing no organopolysiloxane group is formed by polymerizing a (b-3) (meth) acrylic acid alkyl ester monomer.

(In equation (1), n represents an integer of 5 to 500.)
The polyvinyl chloride resin composition according to claim 1, wherein the component (A) contains 5 to 150 parts by mass of the plasticizer (C) with respect to 100 parts by mass.
The polyvinyl chloride resin composition according to claim 1 or 2, wherein the filler (D) is contained in an amount of 50 to 150 parts by mass with respect to 100 parts by mass of the component (A).