JPH0386734A - Foamed polyvinyl chloride resin composition - Google Patents

Abstract

PURPOSE:To prevent the cell collapse and improve the adhesion with a polyurethane foam by compounding a polyvinyl chloride resin, a specific polyester resin, and a blowing agent. CONSTITUTION:A dicarboxylic acid component contg. 50mol% or higher adipic acid is reacted with a glycol component pref. comprising a 2-6C aliph. glycol to give a polyester resin solid at room temp. with a mol.wt. of 600-10000, a hydroxyl value of 3-60, and a softening point (ring and ball method) of 150 deg.C or lower. 100 pts.wt. polyvinyl chloride resin, 1-40 pts.wt. said polyester resin, 0.5-20 pts.wt. blowing agent pref. comprising azodicarbonamide or azobisisobutyronitrile, and, if necessary, an antistatic agent, a lubricant, a plasticizer, a stabilizer, a UV absorber, a filler, a colorant, etc., are compounded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a foamed polyvinyl chloride resin composition that has excellent adhesion to foamed or non-foamed polyurethane and has controlled foam cells.

[Prior Art] Since PVC has excellent chemical, physical and mechanical properties, it is widely used in films, leather, electric wire coatings, water pipes, construction materials, automobiles, materials related to light electrical appliances, etc. Among these wide range of uses, construction materials, automobiles,
In the field of light electrical appliances, insulation, lightweight, soundproofing, shock absorption,
Due to requirements such as vibration isolation, foamed PVC and various foams are often used in a composite form by strongly adhering them. Polyurethane foam is used.

In most cases, the composite of expanded PVC and polyurethane foam is carried out simultaneously with the foaming of polyurethane, regardless of whether it is hard or soft, from the viewpoint of workability and economy.

However, in such a process, the adhesion between foamed PVC and foamed polyurethane is poor, especially with hard foamed polyurethane, and the desired product cannot be obtained. Therefore, in order to obtain strong adhesion, apply an adhesive that has good adhesion to both PVC and urethane foam to the necessary parts of the foamed PvC, such as a synthetic rubber adhesive such as nitrile, butadiene adhesive, or chloroprene adhesive. ,
Apply urethane adhesive, ethylene/vinyl acetate adhesive,
Next, a process is introduced in which foamable polyurethane is injected and foamed and bonded at the same time. However, such a process not only requires a complicated process of applying and drying the adhesive, but also requires consideration of the harmful effects of organic solvents contained in the adhesive. It has drawbacks such as not being able to apply sufficient adhesive to the shaped parts.

On the other hand, for foamed PVC, in order to obtain a high expansion ratio, it is necessary to use a large amount of blowing agent, to obtain a soft texture, to increase the amount of plasticizer, or to use a polyvinyl chloride resin with a low degree of polymerization. However, when foaming, the foam does not form closed cells, and when pressed with a finger, recovery is delayed, resulting in loss of elasticity, and the surface of the molded product becomes rough (air escape).

Problem to be Solved by Invention C] Under these current circumstances, the present inventors have developed a method that can firmly adhere foamed PVC and foamed polyurethane without any pretreatment for adhesion, and that can also bond foamed PVC cells. As a result of intensive research into compositions that can prevent roughness, the present invention has been completed.

[Means for Solving the Problems] That is, the present invention provides 2 parts by weight for 100 parts by weight of PVC (A).
A polyester resin consisting of divalent carboxylic acid and glycol, in which at least 50 mol% or more of the divalent carboxylic acid in the polyester resin is adipic acid, and the softening temperature according to the ring and ball method is 150°C or less, and it is solid at room temperature. Polyester resin (B) J, (1 to 40.0 parts by weight and foaming agent (C) 0.5 to 20 parts by weight)
The cM1 plant is provided.

[Constitution] The PVC (A) used in the present invention is a homopolymer of vinyl chloride, a monomer copolymerizable with vinyl chloride, such as vinylidene chloride, ethylene, propylene, vinyl acetate, or vinyl propionate. Copolymers, vinyl chloride grafted products of ethylene/vinyl acetate copolymers, thermoplastic polyurethane grafted copolymers of vinyl chloride, etc. can be used.

The polyester resin (B) added to the PVC used in the present invention is composed of 2III carboxylic acid and glycol, and at least 50 mol% or more of the divalent carboxylic acid in the polyester is adipic acid, and the ring and ball method It is solid at room temperature with a softening temperature of 150° C. or lower. Examples of divalent carboxylic acids other than adipic acid include aliphatic dicarboxylic acids such as succinic acid, geltaric acid, pimelic acid, speric acid, azelaic acid, sebacic acid, and dodecanedicarboxylic acid, phthalic acid, isophthalic acid, and terephthalic acid. aromatic divalent carboxylic acids and alicyclic divalent carboxylic acids such as tetrahydrophthalic acid or hexahydrophthalic acid, or anhydrides and esters thereof. Of course, these dihydric carboxylic acids can be used alone or in a mixture of two or more.

In addition, examples of glycols used to form the polyester component include ethylene glycol,
-Propylene glycol, l, 3-propylene glycol, 1,2-butylene glycol, l, 3-butylene glycol, 1,4-butylene glycol (1,48G)
, 1,5-bentanediol, neopentyl glycol, 3-methyl-1,5-bentanediol, 1.6-
Hexanediol (1,6HD) or 2-ethyl-1
, 3-hexanediol, and polyalkylene glycols such as diethylene glycol and dipropylene glycol.
Used in mixtures of more than one species. Particularly preferred are aliphatic glycols having 2 to 6 carbon atoms. Especially 1.4 BG, 1.8
HD can be preferably used.

The molecular weight of the polyester resin (B) used in the present invention is preferably 600 to 10,000. In order to obtain stability of cells (cells) in the presence of high temperatures in the foaming process and to obtain uniform void-free closed cells, a range of 1000 to 5000 is preferable.

Such polyester resins (B) are produced by various esterification methods well known to those skilled in the art.

At that time, in order to obtain a polyester having a desired molecular weight, when reacting a dihydric carboxylic acid, a glycol, and, if necessary, a terminal capping agent, selection of their molar ratio is important. For its production, for example, 2
In the presence or absence of a solvent capable of azeotroping water such as toluene or xylene, only the carboxylic acid and the glycol are combined.
Polyester can be obtained by carrying out the reaction at a temperature that allows water produced by esterification to be distilled off.

The polyester resin (B) used in the present invention has a hydroxyl value of 3 to 60 in order to provide adhesiveness with foamed polyurethane (hard, semi-hard, soft). If the hydroxyl value is less than 3, sufficient adhesion to polyurethane foam cannot be obtained when added to PVC, while if it is greater than 60, blooming of the polyester occurs, making it impractical. In particular, those with a hydroxyl value of 8 to 60,
When added to PVC, it has excellent adhesion to polyurethane foam and does not cause blooming.

The amount of the polyester resin (B) of the present invention added to PVC is 1.0 to 40.0 parts by weight per 100 parts by weight of PVC, and is 1.0! If the amount is less than 40.0 parts by weight, the adhesion to polyurethane foam will be poor, and if it exceeds 40.0 parts by weight, a bloom phenomenon will occur. Preferably 5.0-25.
A range of 0 parts by weight is preferred.

The blowing agent (C) used in the present invention is, for example, azocicabonamide, azobisisobutyronitrile, dinitrosopentamethylenetetramine, 4.4°oxybisbenzenesulfonylhydrazide, valatoluenesulfonylhydrazide, etc. organic blowing agents, inorganic blowing agents such as bicarbonate of soda, ammonium carbonate, sodium boron hydride, silicon oxyhydride, etc., methods of foaming by opportunistic stirring, methods of mixing or impregnating with low boiling point volatile solvents and vaporizing, ° liquefaction. These methods include the method of pressurizing gas, the method of incorporating microballoons, and the method of incorporating microcapsules that use vinylidene chloride copolymer as a shell wall and contain low boiling point hydrocarbons, etc.! 11 can be used alone or in combination. This also includes the combined use of urea compounds, zinc white, tribasic lead sulfate, zinc stearate, lead stearate, etc. as decomposition aids.

The blowing agent (C) is particularly preferably an organic blowing agent among the above-mentioned blowing agents, among which azocica-bonamide and azobisisobutyronitrile are useful. The blowing agent (C) is 3 parts by weight.
~15 parts by weight is preferred.

The PVC composition of the present invention may include antistatic agents, lubricants, plasticizers, stabilizers, ultraviolet absorbers, fillers, colorants, antioxidants, blending polymers, pigments, flame retardants, etc. depending on the purpose and use. PvC additives can be added.

Examples of plasticizers include phthalate ester plasticizers such as dioctyl phthalate (DOP), dibutyl phthalate (DBP), and butylbenzyl phthalate (BBP); dioctyl adipate (DOA), and dibutyl adipate (DBA).
), adipate ester plasticizers such as dioctyl sebacate (DO5); sebacate ester plasticizers; trimellitic ester plasticizers; other polyester plasticizers diphosphate ester plasticizers; epoxy plasticizers, Examples include citric acid ester plasticizers, chlorinated paraffins, and chlorinated fatty acid monoesters.

Blend polymers include acrylonitrile-butadiene copolymer, acrylonitrile-butadiene-styrene copolymer (ABS), methyl methacrylate-butadiene-styrene copolymer (MBS), chlorinated polyethylene, ethylene-vinyl acetate copolymer, Post-chlorinated PVC
, NBR1CRSSBR, thermoplastic polyurethane, MM
A Homopolymer Examples include polymers obtained by using or mixing PVc/polyurethane graftomers, polyfunctional acrylic/acrylic monomers, and polymerization catalysts.

The foamed PVc composition of the present invention adheres a foamed polyurethane layer (hard, semi-rigid, soft), but on the other side, it has a layer of polyurethane foam, such as PVC resin, other polymers, paints, fibers, paper, essential materials, etc.
It is not contrary to the spirit of the present invention to provide a layer of material such as metal or non-woven fabric. The foamed PvC composition of the present invention can be obtained by a foaming process from a calender sheet, by so-called powder slush molding, by a PVC plastisol casting method, coating method, or slush method. , any of these molding methods or other methods may be used.

[Effects] The foamed PvC composition of the present invention has excellent adhesiveness with foamed polyurethane, so when combined, it can be used for building materials (insulation, soundproofing, vibration isolation), home appliances, furniture, automobiles (dashboards,
It can be used for a wide range of purposes such as headrests, armrests, etc.

[Example] (Reference Example-1) Adipine v1555 g (3,8Q mol, 75.6 mol% in dibasic acid), terephthalic acid 210, (1,2
7 mol) and 501 g of 1,4-butanediol at 3f!
The mixture was charged into a reaction vessel and heated with a stirrer in a gas stream to raise the temperature to 220°C over 7 hours. After this, dibutyltin oxide in an amount equivalent to 0.02% of the polyester raw material was added as a catalyst, and a reflux condenser was attached to
Heating was continued at a temperature of 20°C. The reaction was carried out for about 7 hours while removing the water produced during this time, to obtain a solid polyester having a hydroxyl value of 25 and a molecular weight of about 4,000.

(Reference Example-2) In Reference Example-1, 402 g of adipic acid (2,75
mol, 51.8 mol% in dibasic acid), terephthalic acid 37
The reaction was carried out in exactly the same manner except that 4 g (2.25 mol>), 98.4 g of t,a-butanediol and 396 g of butanediol were used, and a hydroxyl value of 20 and a molecular weight of about 5 were obtained.
000 solid polyester was obtained.

(Reference Example-3) In Reference Example-1, 146 g of adipic acid (1.0 mol,
2090 mol% in dibasic acid), 592 g of phthalic anhydride (
The reaction was carried out in exactly the same manner except that 495 g of 4,0 mol) and 1,4-butanediol were used, and the hydroxyl value was 30,
A viscous liquid polyester having a molecular weight of about 3,500 was obtained.

(Examples-1 to 3 and Comparative Examples-1 to 2) Reference Examples-1 to 3
Using the polyester obtained in the above, roll cross-wiring (8-inch roll, 140° C. x 10 minutes) was performed with the formulation shown in Table 1 to obtain each PvC sheet with a thickness of 0.5+m.

Next, each of the obtained sheets was foamed to 2.7 times the size at 220° C. for 3 minutes to obtain a foamed sheet.

Next, the unfoamed sheet or foamed sheet is cut to the mold dimensions and placed in the bottom of the mold. After preheating the mold to 40°C or 50°C, the foamable polyurethane material shown in Table 1 is injected, and the mold is heated. The polyurethane foam was sealed and heated and foamed at a predetermined temperature to adhere the foamed polyurethane to the unfoamed sheet or the foamed sheet.

A specimen was taken out from the mold, a specimen measuring 2.5 cm x 15 cm in length was prepared, and the 180 degree peel strength (20 mm/min peeling speed) of the unfoamed sheet, foamed sheet, and foamed polyurethane was measured. At the same time, the surface condition of the foam sheet and the uniformity of the bubbles were evaluated. These results are shown in Table-1.

/ Appearance evaluation criteria for foamed sheets The surface condition is ◎: Very good with no roughness, O: Good with little roughness, Δ: Poor with a little roughness, ×: Very poor with a lot of roughness The condition of the bubbles is ◎: The bubbles are fine and uniform , independent, excellent O: bubbles are slightly uneven Δ: bubbles are uneven, some open cells, slightly inferior ×: bubbles are uneven, there are many open cells, poor - Compounding agents used 1) Tri-2-ethylhexyl trimellitate Dainippon Ink & Chemicals Co., Ltd. pA 2) Epoxidized soybean oil Dainippon Ink & Chemicals Co., Ltd. 3) Ba/Zn powder stabilizer Dainippon Ink & Chemicals Co., Ltd. 4) Foaming agent ( Azoshikabonamide) Made by Hydration Kagaku Co., Ltd. Adhesive urethane foam formulation and foaming conditions *1) Rigid urethane foam formulation and foaming conditions *2) Semi-rigid urethane foam formulation and foaming conditions *3) Polyester-based soft urethane foam formulation and foaming conditions (note) 111prox and TORA L are all made by Dainippon Ink and Chemicals Co., Ltd. As is clear from the examples of results in Table-1, the foamed polyvinyl chloride resin composition of the present invention is The foamed polyvinyl chloride resin composition exhibits excellent adhesion to foamed polyurethane ranging from hard to soft without using any adhesive, and the foamed polyvinyl chloride resin composition has no surface roughness as a foam and has uniform cell conditions. , a product with fine texture and excellent texture was obtained.

Claims (1)

[Claims] 1. For 100 parts by weight of polyvinyl chloride resin (A),
A polyester resin consisting of divalent carboxylic acid and glycol, in which at least 50 mol% or more of the divalent carboxylic acid in the polyester resin is adipic acid, the softening temperature by the ring and ball method is 150 ° C. or less, and the hydroxyl value is 3～
Polyester resin (B) 1 to 60 solid at room temperature
A foamed polyvinyl chloride resin composition comprising 40 parts by weight and 0.5 to 20 parts by weight of a blowing agent (C) as essential components.