JP2615239B2 - Non-adhesive composite resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a polyurethane-polyvinyl chloride-based non-adhesive composite resin composition.

[Conventional technology]

Polyvinyl chloride resin (hereinafter referred to as PVC) is used in many fields as a versatile flexible PVC when used in combination with a low molecular weight plasticizer such as dioctyl phthalate. However, this has a drawback that oil resistance, heat resistance, adhesiveness, and the like are inferior due to extraction and migration of a low molecular weight plasticizer.

Therefore, conventionally, polyurethane resin (hereinafter referred to as PU)
By blending or copolymerizing with PVC, it is known that a sufficiently soft PVC-PU composite resin can be obtained without using a low-molecular-weight plasticizer with easy extraction and migration. I have.

However, in order to obtain a soft PVC-PU composite resin, it is necessary to use a large amount of soft PU. For this reason, it can be obtained by using a large amount of PU
The PVC-PU-based composite resin has various drawbacks, such as strong adhesiveness on the surface. For example, there are problems such as blocking during storage, poor mold separation during hot forming such as injection molding, and poor workability. Also, due to the adhesiveness of the surface, it often cannot withstand actual use as a product. In particular, when a conventional PVC-PU-based composite resin is used for powder molding, the PU component is difficult to melt under no shearing, so that a product having good mechanical properties and surface properties cannot be obtained. . For these reasons, the actual use of the PVC-PU composite resin is often limited despite its excellent physical properties. Therefore, depending on the use, a lubricating agent such as a higher fatty acid or silicone oil, a powdering agent such as talc, and a filler such as calcium carbonate are used to improve the processability and the adhesiveness of the product surface. However, the use of a lubricant causes inconveniences such as poor adhesion and mold contamination due to migration of the lubricant to the surface during molding.
In addition, the use of powdering agents and fillers causes inconveniences such as impairing the transparency of products and deteriorating stain resistance.

In order to solve such inconveniences, using a hydroxy-modified polysiloxane such as a terminal silanol polysiloxane or a terminal alcohol polysiloxane, the following general formula (1) to
(3) (However, in these formulas, Me represents a methyl group, and m is 1 ≦ m
It is an integer of ≦ 450. The group represented by) is introduced into the PU molecule to prevent the lubricant from migrating to the surface, thereby improving the lubricity of the PU.

[Problems to be solved by the invention]

However, the general formula (1), (2) or (3)
The PVC-PU composite resin using a PU having a group represented by the formula (1) has little effect of preventing blocking and improving mold releasability, and has a remarkable adhesion property, which is a great feature of the PVC-PU composite resin. Produces damaging results.

The present invention improves the surface tackiness without impairing the excellent properties of the PVC-PU composite resin, such as heat resistance, oil resistance, and adhesiveness, by extrusion molding, injection molding, compression molding, vacuum molding, In mold processing such as blow molding, it prevents mold contamination and improves mold releasability, and also improves blocking properties during product storage, as well as cold shock resistance and fogging resistance (that is, prevention of oil film formation on the glass surface). It is an object of the present invention to provide a non-adhesive composite resin composition having excellent heat resistance and applicable to powder sintering molding.

[Means for solving the problem]

According to the present invention, there is provided a PVC-PU-based non-adhesive composite resin composition which is excellent in the above-mentioned properties and which can be particularly applied to powder sintering molding.

That is, the non-adhesive composite resin composition of the present invention comprises (A) a diisocyanate compound, (B) a dicarboxylic acid, and 3-methyl-1,5-pentanediol and / or 2-methyl-1,8-octanediol. And a polyester polyol obtained by reacting a diol containing 30 mol% or more in total or less than 70 mol% of other short-chain diols, respectively, and (C) a general formula (I) (Where, Me represents a methyl group, and n is 1 ≦ n ≦ 10
X and Y are 1 ≦ X ≦ 3, 0 ≦ Y ≦ 2
And X + Y = 3, and R represents an alkylene group which may be linked by one or more alkyleneoxy groups. ) Containing PU and PCV obtained by reacting a diol polysiloxane having one terminal.

The one-terminal diol polysiloxane used in the present invention is obtained by subjecting a polysiloxane having a hydrogen substituent terminated by trichlorosilane, methyldichlorosilane, dimethylchlorosilane or the like to an addition reaction with a compound exemplified below. Obtainable.

The number average molecular weight of diol polysiloxane at one end is 340
It is preferably from 10,000 to 10,000, and more preferably from 500 to 5,000. In the case of a diol polysiloxane having a number-average molecular weight of 5,000 or more at one end, the amount required to improve the tackiness of the surface of the PVC-PU-based composite resin composition increases, and at the same time, a defect that the adhesion is easily damaged easily occurs. Number average molecular weight 10,000
Above, this tendency becomes stronger.

The amount of the diol polysiloxane at one end is preferably 5% or less based on the PU component of the PVC-PU-based non-adhesive composite resin composition in order to improve surface tackiness and adhesion.
0.1 to 3% is particularly preferred.

The polyester polyol used for forming the PU in the present invention preferably has a number average molecular weight in the range of 300 to 10,000 from the viewpoint of compatibility between the PU and PVC derived therefrom, and has a number of 500 to 8,000. Those having an average molecular weight range are more preferred, and those having a number average molecular weight range of 1,500 to 8,000 are most preferred.

The polyester polyol used in the present invention contains dicarboxylic acid and 3-methyl-1,5-pentanediol and / or 2-methyl-1,8-octanediol each alone or in a total of 30 mol% or more, It is obtained by reacting a diol containing less than 70 mol% of other short-chain diols. Examples of the dicarboxylic acid include adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid. Examples of the short-chain diol include ethylene glycol, 1,2-propanediol, 1,3
-Propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,9-nonanediol, 1,4-cyclohexanedimethanol And aliphatic, alicyclic or substituted aliphatic diols.

Examples of the diisocyanate compound used in the present invention include conventionally known aromatic, aliphatic or alicyclic diisocyanate compounds used for PU, for example, diphenylmethane diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, 4 ,Four'
-Dicyclohexylmethane diisocyanate and isophorone diisocyanate are preferred.

The amount of the diisocyanate compound to be used is preferably 0.5 to 3 in terms of NCO / CH molar ratio, more preferably 0.7 to 1.5, and most preferably 0.7 to 1.1, based on the total OH groups of the polyester polyol and the diol polysiloxane at one end. preferable.

As the PVC used in the present invention, a polymerization degree of at least 600, particularly 700 to 1,300 polyvinyl chloride homopolymer or a copolymer containing vinyl chloride as a main component, for example, vinyl chloride-vinyl acetate copolymer, vinyl chloride And vinyl chloride-containing polymers such as ethylene-vinyl acetate copolymer. If necessary, this PVC has a stabilizer, lubricant,
Additives such as coloring agents can be added.

Further, in the present invention, a thermoplastic resin or rubber other than PU compatible with PVC, for example, an acrylic resin, a styrene resin, an ABS resin, a nitrile rubber, or the like may be used in combination with a polymer blend vinyl chloride which is previously blended with PVC. it can.

Further, in the present invention, from the viewpoint of improving the surface tackiness of the composite resin composition, the adhesiveness and the meltability during sintering, the mixing ratio of the PVC component and the PU component is 100/1000 to 100/10.
Is preferably 100/200 to 100/20, more preferably 100/150 to 100/50.

In the present invention, a plasticizer can be used in combination to supplement the surface tackiness, adhesiveness and meltability of the composite resin composition, but the amount used is long-term durability, from the viewpoint of ensuring fogging resistance, the composite is used. It is desirable that the amount be 20 parts by weight or less based on 100 parts by weight of the resin.

The plasticizer that can be used in the present invention is usually PVC
Esters, trimellitates, dibasic esters, adipic polyesters, epoxy compounds, inorganic acid esters, glycol esters, such as dioctyl phthalate, trimellit used as plasticizers for Examples thereof include dioctyl acid, di-2-ethylhexyl adipate, di-2-ethylhexyl azelate, soybean oil epoxidized, linseed oil epoxidized, tricresyl phosphate, tributoxyethyl phosphate, and dibutyldiglycol adipate.

A powdering agent may be added to the composite resin composition of the present invention. Preferred powdering agents include PVC having a particle size of 1 to 10 μm. PVC having a degree of polymerization of 1,700 or more or a crosslinked structure can also be used.

The composite resin composition of the present invention has, for example, a particle size of 50 to 500 μm.

The non-adhesive composite resin composition of the present invention includes, for example, a method of reacting a diol polysiloxane having one terminal represented by the general formula (I), a polyester polyol, a diisocyanate compound, and PVC, represented by the general formula (I) Diol polysiloxane at one end, polyester polyol, diisocyanate compound to react to form PU, then formed PU and PV
C, and a diisocyanate compound is first reacted with a diol polysiloxane having one terminal represented by the general formula (I), and then reacted with a polyester polyol to obtain a PU.
And a method of blending the formed PU and PVC.

The blending of PU and PVC may be mixing without solvent, mixing in the form of a solution using a solvent, or mixing in the form of an emulsion.

That is, the PVC-PU non-adhesive composite resin composition of the present invention is obtained by combining PVC, a diol polysiloxane having one terminal represented by the general formula (I), a polyester polyol and a diisocyanate compound at once or in any combination. And by a sequential reaction in the order described above.

[Effects of the Invention] According to the present invention, various properties such as toughness, abrasion resistance and solvent resistance of PU and various properties such as weather resistance and easy processability of PVC are obtained, and heat resistance and adhesiveness are improved. There is provided a non-adhesive composite resin composition of a PVC-PU system which is excellent and has greatly improved surface adhesion. Further, the non-adhesive composite resin composition of the present invention has fogging resistance in addition to the above-described properties,
It has impact resistance at low temperatures and excellent processing characteristics (meltability, mold fouling, etc.) during powder sintering molding, and has the conflicting properties that have been difficult to solve conventionally.

The non-adhesive composite resin composition of the present invention has an extremely wide range of applications such as films, sheets, leathers, tubes, hoses, wrap films, electric wire coatings, coating agents, and paints. In particular, in the case of conventional soft PVC-PU composite resin sheets and films, the workability in the next process occurs due to the sticking of the sheet or film after winding, and the excellent properties cannot be fully utilized as actual products. However, the present invention can greatly improve this point. In addition, since the releasability from a mold is good at the time of molding various products by extrusion molding, injection molding, compression molding, vacuum molding, blow molding, etc., production efficiency can be greatly improved. On the other hand, when the non-adhesive composite resin composition of the present invention is used as a surface material having a hard plastic as a core material, retention of adhesiveness is an important factor. In particular, the composition of the present invention is formed by powder sintering to form a large molded article having a complicated shape, for example, an interior molded article for a vehicle,
A large-sized high-performance instrument panel can be efficiently produced.

As described above, the present invention has a great significance that the range of application to various products is remarkably wide.

〔Example〕

Hereinafter, the present invention will be described more specifically with reference to examples. In the following Examples and Comparative Examples, “parts” means “parts by weight”.

Reference Example 1 1,360-hexanediol 2,360 g (20 mol), 3-methyl-1,5-pentanediol 2,360 g (20 mol), neopentyl glycol 1,060 g (10 mol) and adipic acid 6,6
Add 512 g (44.6 mol) to a reactor with 15 decomposers,
Next, 0.2 g of tetrabutyl titanate was added thereto,
After dehydration at 200 ° C for 12 hours at normal pressure,
A vacuum dehydration reaction was performed at 00 ° C. for 12 hours.

10,680 g of a polyester polyol (hereinafter referred to as PE-1) having an acid value of 0.2 and a hydroxyl value of 55.9 (number average molecular weight of 2,000) was obtained.

Reference Examples 2 to 6 Polyester polyols were obtained in the same manner as in Reference Example 1, except that the diols and dicarboxylic acid of Reference Example 1 were respectively changed.

The raw materials used, their molar ratios (mol%) and the number average molecular weight of the polyester polyol as the product are summarized in Table 1.

Reference Example 7 General formula 17 g of hexamethylene diisocyanate was added to 2 g of a diol polysiloxane having a number average molecular weight of 2,000 and having a number average molecular weight of 2,000 under stirring, and reacted at 75 ° C. for 4 hours. The resulting solution is called PS-1.

Reference Example 8 In Reference Example 7, instead of the one-terminal diol polysiloxane represented by the above general formula, a general formula The reaction was carried out in the same manner as in Reference Example 7, except that a diol polysiloxane having a number average molecular weight of 2,000 and a tolylene diisocyanate was used in place of hexamethylene diisocyanate. The resulting solution
It is called PS-2.

Comparative Reference Example 1 In Reference Example 7, instead of the one-terminal diol polysiloxane represented by the above general formula, a general formula The reaction was carried out in the same manner as in Reference Example 7, except that 2 g of a modified polysiloxane having a number average molecular weight of 5,000 and having OH groups at both terminals was used. The resulting solution is called PS-3.

Example 1 (1) 100 parts of PVC powder having an average polymer of 1,000 were charged into a Hensiel mixer, and 9.8 parts were separately added to 90 parts of PE-1 previously heated to 70 ° C. while stirring and mixing at a rotation speed of 1,000 rpm. P
The mixed solution obtained by adding S-1 and stirring at high speed for 1 minute was put into this Hensiel mixer.

Further, 4 parts of a Ba-Zn-based PVC stabilizer was added thereto, and the mixture was stirred for 1 hour while keeping the internal temperature of the Hensiel mixer at 80 ° C. Then, the internal temperature was lowered to 40 ° C. or lower, 10 parts of PVC for paste (average degree of polymerization: 700) was added, and the mixture was stirred and mixed for 2 minutes to obtain a powdery substance.

 This powdery substance was classified using a 32 mesh sieve.

The yield of the powder obtained excluding the particulate matter on the sieve was 98%.

(2) The obtained powder was subjected to powder sintering at 220 ° C. for 1 minute to obtain a sheet having an average thickness of 0.8 mm on a textured plate having a nickel surface and a copper laminated back surface.

Example 2 100 parts of PVC powder having an average degree of polymerization of 1,000 were put into a Hensiel mixer, and while stirring and mixing at a rotation speed of 1,000 rpm, 20 parts of TRIMERIT were separately added to 70 parts of PE-2 previously heated to 70 ° C. A mixture obtained by adding dioctyl acid, 1 part of 1,4-butanediol and 5 parts of PS-1 and stirring at a high speed for 1 minute,
It was charged into this Hensiel mixer.

Thereafter, in the same manner as in Example 1, a sheet having an average thickness of 0.8 mm was obtained.

Example 3 100 parts of PVC powder having an average degree of polymerization of 1,000 was put into a Hensiel mixer, and while stirring and mixing at a rotation speed of 1,000 rpm, 20 parts of TRIMERIT were separately added to 70 parts of PE-3 previously heated to 70 ° C. A mixture obtained by adding dioctyl acid and 6.3 parts of PS-1 and stirring at high speed for 1 minute was charged into the Hensiel mixer.

Thereafter, in the same manner as in Example 1, a sheet having an average thickness of 0.8 mm was obtained.

Example 4 In Example 3, PE-3 was replaced with PE-4, and 6.3 parts of PS-
A sheet having an average thickness of 0.8 mm was obtained in the same manner as in Example 3, except that 1 was changed to 7.7 parts of PS-2.

Example 5 In Example 3, PE-3 was changed to PE-5, and PS-1 was replaced with PE-5.
Average thickness in the same manner as in Example 3 except that 7.6 parts were used.
A 0.8 mm sheet was obtained.

Example 6 In Example 3, PE-3 was replaced with PE-6, and PS-1 was replaced with PE-6.
Except that 3.3 parts were used, the average thickness was 0.8 in the same manner as in Example 3.
mm sheet was obtained.

Comparative Example 1 A sheet having an average thickness of 0.8 mm was obtained in the same manner as in Example 3, except that 6.3 parts of PS-1 was changed to 4.8 parts of hexamethylene diisocyanate.

Comparative Example 2 In Example 3, except that PS-1 was changed to PS-3.
In the same manner as in Example 3, a sheet having an average thickness of 0.8 mm was obtained.

Comparative Example 3 100 parts of PVC powder having an average degree of polymerization of 1,000 was put into a Hensiel mixer, and 80 parts of dioctyl trimellitate and a Ba / Zn-based PVC stabilizer 4 were stirred and mixed at a rotation speed of 1,000 rpm. Of Hensiel mixer
The mixture was stirred for 1 hour while maintaining the temperature at 100 ° C. Next, set the internal temperature to 4
The temperature was lowered to 0 ° C. or lower, 10 parts of PVC for paste (average degree of polymerization: 700) was added, and the mixture was stirred and mixed for 2 minutes to obtain a powdery substance.

Next, a sheet having an average thickness of 0.8 mm was obtained in the same manner as in Example 1 using this powdery substance.

[Performance measurement method]

 Table 2 shows the results of the following performance measurements.

1. Meltability In Examples 1 to 6 and Comparative Examples 1 to 3, water cooling was immediately performed after powder sintering molding (220 ° C. × 1 minute), and the molten state and uneven thickness of the rear surface (non-metal surface) of the molded sheet at that time The presence or absence was visually determined.

 These determination results are represented in the following three stages.

○ Smoothly melted and no uneven portion △ Incomplete melting × Incomplete melting and large uneven thickness 2. Mold releaseability In Examples 1 to 6 and Comparative Examples 1 to 3, powder sintering was performed, water-cooled and then molded. A 2 cm wide cut was made in the sheet, and the release force (g / cm) at 180 ° inversion was measured.

 These measurement results are represented in the following two stages.

○ Less than 50 g / cm × 50 g / cm or more 3. Mold stainability The same powder was repeatedly sintered and molded 10 times, and the luminance of the mold surface of the sheet obtained at the 10th time was visually determined.

 These measurement results are represented in the following two stages.

○ Same as the first time × Brightness greater than the first time 4. Adhesiveness Using the sheets obtained in Examples 1 to 6 and Comparative Examples 1 to 3, an integrally molded flat plate of the sheet and the polyurethane foam was produced.

The adhesion (adhesion) between the sheet and the foam of the obtained molded article was measured by a 180-degree peel test. These measurement results are represented in the following two stages.

○ 300g / cm or more × less than 300g / cm 5.Durability Put the integrally molded flat plate in a gear oven and put it at 500
After the elapse of time, measure the elongation of the sheet according to JIS K6723,
This is expressed in terms of elongation retention (%) compared to the initial one.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication location C08L 75:06) (C08L 75/06 27:04) (56) References JP-A-62-220553 (JP, A) JP-A-62-205116 (JP, A) JP-A-62-195389 (JP, A) JP-A-61-120820 (JP, A) JP-A-1-254725 (JP, A)

Claims (1)

(57) [Claims] 1. A non-adhesive composite resin composition containing a polyurethane and polyvinyl chloride, wherein the polyurethane comprises (A) a diisocyanate compound, (B) a dicarboxylic acid, and 3-methyl-1,5 A polyester polyol obtained by reacting pentanediol and / or 2-methyl-1,8-octanediol, alone or in total, with a diol containing 30 mol% or more and another short-chain diol of less than 70 mol%, And (C) a general formula (I) (Where, Me represents a methyl group, and n is 1 ≦ n ≦ 10
X and Y are 1 ≦ X ≦ 3, 0 ≦ Y ≦ 2
And X + Y = 3, and R represents an alkylene group which may be linked by one or more alkyleneoxy groups. The composition is characterized by being a polyurethane obtained by reacting a diol polysiloxane having one terminal represented by the formula (1).