JPS6264861A - Polyvinylchloride-polyurethane composite resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. having excellent low-temp. flexibility and hydrolysis resistance and exhibiting excellent flexibility for a long period of time, comprising a PVC and a polyurethane having a specific group. CONSTITUTION:The titled compsn. comprises a PVC and a polyurethane having a group of formula I or II in the molecule. The polyurethane has a good compat ibility with the PVC and excellent plasticizability and is obtained by using a polyesterpolyol contg. said group and having an average MW of 1,000-10,000. For example, the polyurethane used is obtd. by reacting a block polyester contg. as at least one component a poly(beta-methyl-delta-valerolactone)polyol having an average MW OF 1,000-10,000 obtd. by the ring-opening polymn. of beta-valero lactone or a mixed lactone of 10mol% or more of it and another lactone, with an org. polyisocyanate. The resulting composite resin compsn. has a hydrolysis resistance and an excellent low-temp. flexibility and exhibits an excellent flexibil ity for a long period of time.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a composite resin composition comprising polyurethane and polyvinyl chloride.

Conventional technology Conventionally, plasticizers for polyvinyl chloride (hereinafter sometimes abbreviated as vinyl chloride) include low-molecular esters such as phthalate, polybutylene adipate polyols or polyhexamethylene adipate, and organic polyinsyanates. Examples include polyurethane, but the most widely used are heptatal acid ester derivatives such as dioctyl phthalate. Although these phthalate esters have excellent plasticizing performance, they have high extractability, migration properties, etc., and are easily extracted by gasoline, oil, or other organic chemicals. Therefore, polyurethane has been blended or copolymerized with polyvinyl chloride to create sufficiently soft polyvinyl chloride compositions without using the above-mentioned PVC plasticizers, which are easily extracted and migrated. is known to be obtained.

Problems to be Solved by the Invention When the above-mentioned polyurethane is used as a plasticizer for PVC, the plasticizing ability of the polyurethane is still insufficient, and a large amount of polyurethane must be used to obtain a soft PVC composition. Alternatively, they had to be used in combination with other low-molecular plasticizers.

Furthermore, since the polyurethane used as a plasticizer has poor hydrolysis resistance, the performance of the composite resin composition tends to change over time, which is undesirable.

Further, the polyvinyl chloride composition containing the above-mentioned polyurethane was not sufficiently satisfactory in flexibility under a low temperature atmosphere (hereinafter referred to as low temperature flexibility).

The object of the present invention is to create a soft thermoplastic that has excellent flexibility over a long period of time without extractability or migration by combining a special polyurethane with an excellent plasticizing ability that has never been seen before and PVC. An object of the present invention is to provide a resin composition.

This is achieved by a composition consisting of: Polyurethane having good compatibility with PVC and excellent plasticizing ability is produced by using a polyester polyol containing the above groups and having an average molecular weight of 1.000 to 10,000, and has an average molecular weight of 1.00.
0 to 10,000 polyol specifically refers to poly(
β-methyl-δ-valerolactone) polyol or a polyol mixture containing it, or β-methyl-δ-
It is a block or random copolymerized polyol having an average molecular weight of i, ooo to in, 000 obtained by ring-opening copolymerization using valerolactone as one component.

Poly(β-methyl-δ-valerolactone) polyol is obtained by ring-opening polymerization of β-methyl-δ-valerolactone with a low molecular weight polyhydric alcohol such as ethylene glycol or butanediol.

Furthermore, there are copolymers with other lactones, such as those obtained by ring-opening copolymerization of ε-caprolactone and β-methyl-δ-valerolactone, or copolymers of adipate polyester polyols and β-methyl-δ-valerolactone. Even when a block polymer polyol other than valerolactone is used, the same effect as described above can be obtained.

In the present invention, the average molecular weight of the polyol is CH2.
Examples of polyols that can be used in combination with polyols having a C group include 3-methyl-1,5-bentanediol or and a low molecular polyol containing this.

Adipic acid, succinic acid, glutaric acid, pimelic acid.

03-Methyl-1 is a polyester polyol synthesized from dicarboxylic acids such as cepatic acid, azelaic acid, terephthalic acid, isophthalic acid, maleic acid, and phthalic acid.
, 5-bentanediol and the like are preferably 1,6-hexanediol, 1,4-butanediol, 1,9-nonanediol, and the like. In the present invention, at least 10 moles of 3-methyl-
Preferably it is 1,5-bentanediol.

The organic polyisocyanate used in the present invention includes:
For example diphenylmethane diisocyanate, 2.4-1
lylene diisocyanate, 2.6-) lylene diisocyanate, phenylene diisocyanate, 1,5-naphthylene diisocyanate, 3゜3'-dichloro-4,4'
- Aromatic diisocyanates such as diphenylmethane diisocyanate, xylylene diisocyanate, and toluylene diisocyanate, and aliphatic or alicyclic diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and hydrogenated xylylene diisocyanate. can be mentioned. Preferred diisocyanates are aliphatic or cycloaliphatic diisocyanates, and particularly preferred are hexamethylene diisocyanate and 4,4'-dicyclohexylmethane diisocyanate. These diisocyanates may be used alone or in combination.

The method for producing a composite resin composition of polyvinyl chloride and polyurethane is as follows: (1) thermoplastic polyurethane and polyvinyl chloride are mixed together using a mixing device such as an extruder roll using a method called polymer blending. (2) A method in which a thermoplastic polyurethane soluble in vinyl chloride monomer is dissolved in the vinyl chloride monomer, and then the vinyl chloride monomer is radically polymerized. (3) A method in which powdered polyvinyl chloride is mixed with polyurethane while stirring. Examples include a method of impregnating polyester glycol, which is a raw material, and adding polyisocyanate to it to produce polyurethane in polyvinyl chloride (4) A method of producing a mixed emulsion of a polyvinyl chloride emulsion and a polyurethane emulsion. .

In the present invention, the amount of the urethane component is 10 to 200 parts by weight per 100 parts by weight of the vinyl chloride component.

The polyvinyl chloride used in the present invention is a vinyl chloride-containing polymer, and includes a polyvinyl chloride homopolymer with a degree of polymerization of 600 or more or a copolymer containing vinyl chloride as a main component. Examples include vinyl-ethylene vinyl acetate (EVA) copolymer. In the production of the composite resin of the present invention, stabilizers, lubricants, fillers, plasticizers, colorants, etc. can be blended in advance.

The composition of the present invention has both the properties of thermoplastic polyurethane, such as toughness, abrasion resistance, and solvent resistance, and the properties of vinyl chloride polymer, such as weather resistance and easy moldability, as well as excellent impact resilience and transparency. Film,
sheets, leather, tubes, hoses, wrap films,
It has a wide range of applications including backing, wire coating, rice cakes, adhesives, coatings, binders, and paints.

Example Hereinafter, the present invention will be explained in more detail with reference to Examples.

Parts in Examples and Comparative Examples indicate parts by weight. Each physical property in Examples and Comparative Examples was measured by the following test method. The results are summarized in Table 1.

Test method; (1) Low-temperature flexibility test piece with a thickness of 0.41 flll is prepared using a direct-reading dynamic viscoelasticity measuring device made by Toyo Sokki, Pyblon Model DDV-I.
(110H2) is measured. The smaller Ta is, the better the low-temperature flexibility is.

(2) Rate of change in flexibility over time One day after molding, the 20 thymomodulus was measured at a tensile speed of 50 n/min according to the JIS K-6 tensile test method, and the modulus was A, 60 after molding. The rate of change over time was calculated using the following formula, assuming that 20 thymodilus after one day had passed is A60. Rate of change over time (@= ((A60-A1)/A11
1 n.

Example 1 Hexamethylene diisocyanate 1.1 was added to a polyester glycol with an average molecular weight of 4,000 from a mixed diol of 3-methyl-1,5-bentanediol and 1,9-nonanediol (3/7) and adipic acid. mol was added under stirring, and after high-speed stirring, the mixture was spread on a vat in a dryer at 140°C and reacted for 30 minutes to complete the reaction. After mixing 100 parts of powdered polyvinyl chloride with a degree of polymerization of 1.000 with 100 parts of this polyurethane and kneading the mixture at 150°C for 10 minutes,
It was pressed into a sheet of a predetermined thickness.

Example 2 0.1 mol of poly(β-methyl-δ-valerolactone) glycol with molecular weight <S, 000 and 0.9 mol of polyester glycol with molecular weight 2,000 obtained from 1,9-nonanediol and adipic acid. Add 1.05 mol of hexamethylene diisocyaner to the mixed glycol, stir at high speed, and spread in a vat of a dryer at 140°C.
The reaction was carried out for 0 minutes, and the mixture was cooled to -40°C and then ground. 100 parts of this polyurethane, 100 parts of vinyl chloride monomer,
300 parts of water, α,α′-azobisisobutyronitrile 0
．． 5 parts of polyhinyl alcohol and 0.5 parts of polyhinyl alcohol were placed in an autoclave and stirred at room temperature for 3 hours to dissolve the polyurethane.
Then, polymerization was carried out at 60°C for 10 hours. The obtained suspended product was dried at 140° C. under reduced pressure to obtain a powder.

After adding stabilizers such as calcium stearate and zinc stearate, the mixture was kneaded on a roll for 5 minutes and formed into a sheet.

Comparative Example 1 A sheet was produced in the same manner as in Example 1 except that only the soft segment of the polyurethane in Example 1 was changed to a polyester glycol having a molecular weight of 4,000 made from 1,6-hexanediol and adipic acid.

Comparative Example 2 A sheet was produced in the same manner as in Example 2 except that only the soft segment of the polyurethane in Example 2 was replaced with polycaprolactone glycol having a molecular weight of 4,000.

Table 1 Effects of the Invention The polyvinyl chloride-polyurethane composite resin composition of the present invention has excellent low-temperature flexibility and hydrolysis resistance, so it has excellent flexibility over a long period of time.

Claims (3)

[Claims] (1) Polyvinyl chloride and ▲ mathematical formula, chemical formula,
A polyvinyl chloride-polyurethane composite resin composition consisting of a polyurethane having a ▼ group or a ▼ mathematical formula, chemical formula, table, etc. (2) The polyurethane is a polyurethane having an average molecular weight of 1,000 to 10,000 obtained by ring-opening polymerization of β-methyl-δ-valerolactone alone or a mixed lactone containing 10 mol% or more of this lactone. The composition according to claim 1, which is a polyurethane obtained by reacting a (β-methyl-δ-valerolactone) polyol or a block polyester containing the polyol as at least one component with an organic polyisocyanate. (3) The polyurethane is a polyester polyol with an average molecular weight of 1,000 to 10,000 obtained from 3-methyl-1,5-pentanediol alone or a mixed diol containing 10 mol% or more of the diol and dicarboxylic acid, and an organic The composition according to claim 1, which is a polyurethane obtained by reacting a polyisocyanate.