JP6385219B2 - Vinyl chloride resin composition for foam molding - Google Patents

Description

The present invention relates to a foamed vinyl chloride resin composition excellent in foamability (foaming ratio, foamed cell state of an extruded foamed product) during molding, and excellent in extrusion moldability with little cracking, and foams the resin composition. The present invention relates to a molded foam product.

Vinyl chloride resin compositions are excellent in mechanical properties, physical properties, electrical properties, moldability, and the like, and are therefore used in a wide variety of applications. For example, a foamed molded product of a vinyl chloride resin composition has been studied as a material that replaces wood used for building materials and furniture.

Patent Document 1 states that “a copolymer of 0.1 to 5 parts by weight of acrylonitrile-butadiene rubber dissolved in methyl ethyl ketone in an amount of 5 to 90% by weight based on 100 parts by weight of vinyl chloride resin, and methyl methacrylate as a main component. A soft vinyl chloride resin composition comprising 1 to 60 parts by weight of a methyl methacrylate copolymer having a specific viscosity of 2.5 or more measured at 30 ° C. in a 100 ml benzene solution containing 4 g and 20 to 200 parts by weight of a plasticizer. In paragraph 0022, as a plasticizer, “aroma such as dibutyl phthalate, dioctyl phthalate, diisodecyl phthalate, diisononyl phthalate, diundecyl phthalate, trioctyl trimellitate, triisooctyl trimellitate” is disclosed. Alkyl esters of polybasic acids, dibutyl adipate, geo Alkyl esters of aliphatic polybasic acids such as til adipate, diisononyl adipate, dibutyl azelate, dioctyl azelate, diisononyl azelate, phosphoric acid alkyl esters such as tricresyl phosphate, polyester plasticizers, epoxy plasticizers , Chlorinated paraffin, etc. ".

However, in recent years, the demand for vinyl chloride resin compositions not containing phthalic acid plasticizer as a main component has increased due to the increasing environmental problems in the world.

Therefore, “obtained by esterification of 1,2-cyclohexanedicarboxylic acid or its anhydride and an aliphatic monohydric mixed alcohol having 4 to 13 carbon atoms containing a branched alcohol having 9 carbon atoms as an essential component. 1,2-cyclohexanedicarboxylic acid diester, the content of the branched alcohol having 9 carbon atoms in the aliphatic monohydric mixed alcohol is 70 to 97% by weight, other than the branched alcohol having 9 carbon atoms It has been proposed to use a plasticizer for vinyl chloride resin containing 1,2-cyclohexanedicarboxylic acid diester characterized in that the content of alcohol is 3 to 30% by weight (Patent Document 2). . However, there is no description or suggestion about a technique for obtaining a vinyl chloride resin composition excellent in extrusion foam moldability.

JP-A-6-192457 JP 2001-207002 A

The present invention has been made in view of such a situation, and the problem is that, in extrusion foam molding, uniform and fine foam cells are formed at a sufficiently high foaming ratio, and there is little generation of eyes. Therefore, an object of the present invention is to provide a vinyl chloride resin composition for foam molding which can obtain a molded product having uniform and fine foam cells and a smooth and beautiful surface appearance, and a molded product containing the composition.

As a result of intensive studies, the present inventor has found that the above problems can be achieved by a vinyl chloride resin composition containing a specific plasticizer.

That is, the present invention
Component (a) 100 parts by mass of vinyl chloride resin;
Component (b) casNo. Cycloisomer-1,2-dicarboxylic acid di (isononyl) ester 15 to 90 mol% obtained by hydrogenation of 28553-12-0 phthalic acid diisononyl ester 90 to 100 mol%, trans isomer 10 to 0 mol% 150 parts by mass; and component (c) blowing agent 0.01-10 parts by mass;
Is a vinyl chloride resin composition for foam molding.

A second invention is a building material including the resin composition according to the first invention.

A third invention is a deck, a door frame, a bay window frame or a baseboard containing the resin composition described in the first invention.

In the extrusion foam molding, the vinyl chloride resin composition of the present invention is formed with uniform and fine foam cells at a sufficiently high foaming ratio, and is less likely to cause eyes. Therefore, by extrusion foam molding of the vinyl chloride resin composition of the present invention, molded products having uniform and fine foam cells and a smooth and beautiful surface appearance, such as decks, door frames, bay window frames, and baseboards. Building materials such as; frame; furniture;

Component (a) “vinyl chloride resin” (essential component):
The vinyl chloride resin used as component (a) of the present invention refers to all polymers having a group represented by —CH ₂ —CHCl—, a vinyl chloride homopolymer; a vinyl chloride / vinyl acetate copolymer. , Vinyl chloride / (meth) acrylic acid copolymer, vinyl chloride / (meth) methyl acrylate copolymer, vinyl chloride / (meth) ethyl acrylate copolymer, vinyl chloride / maleic acid ester copolymer, chloride Vinyl / ethylene copolymer, vinyl chloride / propylene copolymer, vinyl chloride / styrene copolymer, vinyl chloride / isobutylene copolymer, vinyl chloride / vinylidene chloride copolymer, vinyl chloride / styrene / maleic anhydride ternary Copolymer, vinyl chloride / styrene / acrylonitrile terpolymer, vinyl chloride / butadiene copolymer, vinyl chloride / isoprene copolymer Copolymerized with vinyl chloride and vinyl chloride, such as vinyl chloride / chlorinated propylene copolymer, vinyl chloride / vinylidene chloride / vinyl acetate terpolymer, vinyl chloride / acrylonitrile copolymer, vinyl chloride / various vinyl ether copolymers, etc. Copolymers with other possible monomers; Post-chlorinated vinyl copolymers and other vinyl chloride homopolymers and modified vinyl chloride copolymers; and structurally vinyl chloride resins such as chlorinated polyethylene And similar chlorinated polyolefins.

The component (a) has a number average polymerization degree of preferably 300 to 7000, more preferably 1000 to 2500, from the viewpoints of the expansion ratio at the time of extrusion foam molding, the foamed cell form, and the eyes.

As the component (a), one or a mixture of two or more of these vinyl chloride resins can be used.

Component (b) “cyclohexane-1,2-dicarboxylic acid having 90 to 100 mol% of cis isomer and 10 to 0 mol% of trans isomer obtained by hydrogenation of diisononyl phthalate of cas No. 28553-12-0 Di (isononyl) ester "(essential component):
The vinyl chloride resin composition of the present invention comprises component (b) casNo. 28553-12-0 phthalic acid diisononyl ester (hereinafter sometimes abbreviated as DINP) obtained by hydrogenation of 90 to 100 mol% of cis isomer, 10 to 0 mol% of cyclohexane-1, 2-dicarboxylic acid di (isononyl) ester. Since the component (b) is obtained by hydrogenating DINP, the resin composition of the present invention can form uniform and fine foam cells at a sufficiently high foaming ratio in extrusion foam molding, There will be less generation of eyes.

The DINP is not particularly limited, and DINP synthesized by a known method can be used.

The component (b) is a mixture of 90 to 100 mol% of cis isomer and 10 to 0 mol% of trans isomer. For this reason, the resin composition of the present invention is such that uniform and fine foam cells are formed at a sufficiently high foaming ratio in extrusion foam molding, and there is little generation of eyes. A mixture of 95 to 100 mol% of cis isomer and 5 to 0 mol% of trans isomer is preferable. Here, the sum of the cis isomer and the trans isomer is 100 mol%.

The mixture of the cis isomer and the trans isomer can be obtained by hydrogenating DINP by a known method (for example, a technique described in JP 2013-513477 A).

The ratio of the cis isomer to the trans isomer of the component (b) can be determined from a nuclear magnetic resonance spectrum of proton (hereinafter sometimes abbreviated as ¹ H-NMR). The methine proton of dialkyl hexahydrophthalate shows a signal at 2.5-3.0 ppm, of which 2.7-3.0 ppm is in the cis isomer and 2.5-2.7 ppm is in the trans isomer. Be attributed. Thus, the cis isomer ratio is 2.7-3.0 ppm integrated area to 2.5-3.0 ppm integrated area, and the trans isomer ratio is 2.5-3.0 ppm integrated area 2. It can be determined as an integrated area of 5 to 2.7 ppm. The measurement of ¹ H-NMR can be performed with reference to, for example, JP-T-2005-504119. It can also be done by requesting measurements from Mitsui Chemical Analysis Center.

The blending amount of the component (b) is from 15 to 150 parts by mass of the component (b) with respect to 100 parts by mass of the component (a), from the viewpoint of the expansion ratio at the time of extrusion foaming, the foamed cell form, and the eyes. Preferably it is 20-120 mass parts.

In the resin composition of the present invention, the plasticizer other than the component (b), for example, cyclohexane-1, whose ratio of cis isomer to trans isomer is outside the specified range, is not limited to the object of the present invention. 2-dicarboxylic acid di (isononyl) ester, casNo. Cyclohexane-1,2-dicarboxylic acid di (isononyl) ester, phthalic acid ester, trimellitic acid ester, fatty acid dibasic ester, phosphoric acid ester obtained by hydrogenating 68515-48-0 phthalic acid diisononyl ester, One or more epoxy plasticizers and polyester plasticizers may be included.

Component (c) Foaming agent (essential component)
As the foaming agent used as the component (c) of the present invention, both organic and inorganic types can be used.

Preferred examples of the component (c) include azo compounds such as azodicarboxylic acid amide; nitroso compounds such as N, N′-dinitrosopentamethylenetetramine; carbonates such as sodium bicarbonate and ammonium bicarbonate; citric acid, And organic acids such as sodium citrate and succinic acid; and sodium borohydride. It is also preferable to use a combination of carbonate and organic acid. When extrusion foam molding is performed at a relatively high temperature, compounds such as p, p′-oxybisbenzenesulfonyl semicarbazide, p-toluenesulfonyl semicarbazide, trihydrazinotriazine, and barium azodicarboxylate may be used. Good. Of these, azodicarboxylic acid amide is particularly preferred.

The compounding amount of the component (c) is from 0.01 to 10 masses of the component (d) with respect to 100 mass parts of the component (a) from the viewpoint of the expansion ratio at the time of extrusion foaming, the foamed cell form, and the eyes. Parts, preferably 1 to 10 parts by mass.

The resin composition of the present invention may further contain a vinyl chloride resin and a stabilizer usually used for the resin composition. Examples of the stabilizer include organotin compound-based, barium-zinc-based, calcium-zinc-based, and lead-based stabilizers. Among these, from the viewpoint of environmental problems, organotin compound-based, barium-zinc-based, and calcium-zinc-based stabilizers are preferable. As a stabilizer, these 1 type, or 2 or more types of mixtures can be used. As for the compounding quantity of a stabilizer, 0.1-10 mass parts is preferable with respect to 100 mass parts of said components (a).

The resin composition of the present invention may further contain various metal soaps, fatty acids, and lubricants such as polyethylene wax. The blending amount of the lubricant is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the component (a).

In the resin composition of the present invention, the vinyl chloride resin and various additives usually used in the resin composition (for example, heat stabilizer, filler, lubricant, Pigments, ultraviolet absorbers, etc.) and various fillers (for example, calcium carbonate, clay, talc, etc.).

In the resin composition of the present invention, the above component (a), the above component (b), and an optional component used according to necessity are melted and kneaded using an arbitrary melt kneader, It can be obtained by dry blending component (c). Examples of the melt kneader include a single-screw extruder, a twin-screw extruder, a roll, a mixer, various kneaders, and an apparatus in which these are arbitrarily combined. The melt kneading is preferably performed at a resin temperature of 150 to 180 ° C. using a pressure kneader.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these.

Raw materials used Component (a):
(A-1) A vinyl chloride homopolymer having a number average degree of polymerization P = 1050.
(A-2) Vinyl chloride homopolymer having a number average degree of polymerization P = 1400.
(A-3) Vinyl chloride homopolymer having a number average polymerization degree P = 1700.
(A-4) A vinyl chloride homopolymer having a number average polymerization degree P = 2000.
(A-5) A vinyl chloride homopolymer having a number average degree of polymerization P = 2500.

Component (b):
(B-1) A diisononylcyclohexane-1,2-dicarboxylate plasticizer having 92 mol% of cis isomer and 8 mol% of trans isomer obtained by hydrogenating DINP.
(B-2) A diisononylcyclohexane-1,2-dicarboxylate plasticizer having 100 mol% of cis isomer and 0 mol% of trans isomer obtained by hydrogenating DINP.

Comparative component (b ′):
(B′-1) A diisononylcyclohexane-1,2-dicarboxylate plasticizer having 85 mol% of cis isomer and 15 mol% of trans isomer obtained by hydrogenating DINP.
(B′-2) casNo. A diisononylcyclohexane-1,2-dicarboxylate plasticizer containing 95 mol% of cis isomer and 5 mol% of trans isomer obtained by hydrogenating 68515-48-0 phthalic acid diisononyl ester.

Component (c):
(C-1): Mitsubishi Chemical Corporation foaming agent masterbatch "Fine blow S20N (trade name)". Contains 20% by mass of the organic and inorganic mixed foaming agent “Fine Serol 100 (% by mass)” of Mitsubishi Chemical Corporation.
(C-2): Otsuka Chemical Co., Ltd. azodicarboxylic acid amide “Uniform AZ-L8 (trade name)”. Average particle size 11 μm.
(C-3): Sodium bicarbonate foaming agent ““ SC-D (trade name) ”by Eiwa Kasei Kogyo Co., Ltd.

Optional component (d):
(D-1) Dioctyltin mercapto stabilizer “ADEKA STAB 465 (trade name)” by ADEKA Corporation.
(D-2) Barium-zinc composite stability of ADEKA Corporation.
(D-3) A polyethylene wax lubricant “High Wax 4202E (trade name)” manufactured by Mitsui Chemicals, Inc.

(E) Vinyl chloride resin composition for skin material:
(E-1) 100 parts by mass of (a-2), 60 parts by mass of (b-2), 2 parts by mass of (d-2), and 1 part by mass of (d-3) are mixed with a pressure kneader. Was used and melt kneaded under conditions of a resin temperature of 160 ° C. during discharge.

Example 1
100 parts by mass of the component (a-2), 50 parts by mass of the component (b-1), 2 parts by mass of the component (d-2), and 1 part by mass of the component (d-3) are mixed with a pressure kneader. It was used and melt-kneaded under the condition of a resin temperature at discharge of 160 ° C. to obtain a vinyl chloride resin composition. To the obtained vinyl chloride resin composition, 2 parts by mass of the component (c-2) is dry blended with respect to 100 parts by mass of the component (a-2), and the vinyl chloride resin composition for foam molding is used. Got. The following tests (1) to (4) were performed on the obtained vinyl chloride resin composition for foam molding. The results are shown in Table 1.

Test method (1) Eye dispersal during extrusion foaming:
A laminate of a foam base having a thickness of 5 mm and a width of 100 mm and a skin having a thickness of 1 mm and a width of 100 mm is used. The foam base is made of a vinyl chloride resin composition for foam molding, and a φ40 mm extruder is used. Coextruded under conditions of outlet resin temperature of 190 ° C. and screw rotation speed of 40 rpm, using the above (E-1) and φ40 mm extruder, die outlet resin temperature of 160 ° C. and screw rotation speed of 20 rpm. Molded. At this time, the take-up speed was 0.8 m / min. Said extrusion foaming was performed continuously for 4 hours, and the die outlet at that time was visually observed and evaluated according to the following criteria.
◯: No eye discoloration even after 4 hours.
Δ: There is no discoloration before 1 hour. After 1 hour, eyes will be recognized 4 hours later.
×: Eye discoloration is recognized before 1 hour.

(2) Foamed cell form of extruded foam molded product:
The central part of the foamed base material portion in the cross section of the extruded foam molded product obtained in the test (1) was observed using a magnifying glass with memory (10 times) and evaluated according to the following criteria. Here, the cell diameter is an average value obtained by measuring the major axis of 20 adjacent cells, assuming that the foamed cells are elliptical.
A: The cell diameter is 0.1 to 0.2 mm. Each cell is independent.
A: The cell diameter is 0.1 to 0.2 mm. However, a slightly connected cell is observed.
(Triangle | delta): A cell diameter is 0.2 mm or more. In addition, connected cells are allowed.
X: The cell diameter is 0.2 mm or more. In addition, many cells communicate with each other to form a large cavity.

(3) Foaming ratio:
The specific gravity 1 was measured according to the underwater substitution method of JIS K 7112: 1999, using the central part of the foam base material of the extruded foam molded article obtained in the test (1) as a test piece. Next, a 2 mm thick press sheet was prepared using the vinyl chloride resin composition before dry blending the foaming agent, and the specific gravity 2 was measured using this in accordance with the underwater substitution method of JIS K 7112: 1999. The expansion ratio was obtained from the specific gravity 1 and specific gravity 2 by the following formula and evaluated according to the following criteria.
Foaming ratio = specific gravity 2 / specific gravity 1
○: 1.5 or more ×: less than 1.5

Examples 2-18, Comparative Examples 1-2
The same procedure as in Example 1 was performed except that the raw materials used were changed as shown in any one of Tables 1 to 3. The results are shown in any one of Tables 1-3.

In the foamed vinyl chloride resin composition of the present invention, uniform and fine foam cells are formed at a sufficiently high foaming ratio in extrusion foam molding, and there is little generation of eyes.

On the other hand, instead of component (b), Comparative Example 1 using a plasticizer having a cis / trans ratio outside the specified range, and component (b) (DINP (casson. 28553-12-0 phthalate diisononyl ester) Instead of a plasticizer obtained by hydrogenation of casNo. In Comparative Example 2 using a plasticizer obtained by hydrogenating 68515-48-0 phthalic acid diisononyl ester, it is easy to generate eyes in extrusion foam molding, and the foam cell shape is insufficient.

Claims (5)

Component (a) 100 parts by mass of vinyl chloride resin;
Component (b) casNo. Cycloisomer-1,2-dicarboxylic acid di (isononyl) ester 15 to 90 mol% obtained by hydrogenation of 28553-12-0 phthalic acid diisononyl ester 90 to 100 mol%, trans isomer 10 to 0 mol% 150 parts by mass; and component (c) blowing agent 0.01-10 parts by mass;
A vinyl chloride resin composition for extrusion foam molding comprising:
A building material comprising the resin composition according to claim 1.
A deck, a door frame, a bay window frame, or a skirting board comprising the resin composition according to claim 1.
Furniture comprising the resin composition according to claim 1.
A frame containing the resin composition according to claim 1.