JPH0240712B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyester resin adhesive for vinyl chloride resin molded articles. PVC resin molded products including PVC resin sheets, films, leather, foams, etc.
It is widely used in household electrical appliances, cabinets, automobile interiors, house interiors, etc. Polyester resin adhesives are used for a variety of purposes including textile fabrics and metal products, but none of these existing adhesives can be used as adhesives for the vinyl chloride resin molded products. There is no one that has such performance, and there is an urgent need for its development. The present inventors have conducted various studies in view of the above circumstances, and found that aromatic dicarboxylic acid and adipic acid are used as the acid component (A), 1,4-cyclohexanedimethanol and a glycol with a molecular weight of 300 or less (with the exception of 1, A specific polyester resin containing 4-cyclohexanedimethanol (excluding cyclohexanedimethanol) in a specific proportion as the glycol component (B) is excellent as an adhesive between vinyl chloride resin molded products and between vinyl chloride resin molded products and other base materials. The present inventors have discovered that the adhesive has a high adhesive strength and a high adhesive retention rate, and have completed the present invention. Examples of aromatic dicarboxylic acids as the acid component (A) in the present invention include terephthalic acid, isophthalic acid, phthalic acid, lower alkyl esters thereof, and phthalic anhydride. Examples of adipic acid include terephthalic acid, isophthalic acid, phthalic acid, lower alkyl esters thereof, and phthalic anhydride. It also includes things. The glycol component (B) contains 1,4-cyclohexanedimethanol and other glycols having a molecular weight of 300 or less in a ratio of 10:90 to 1:99 (molar ratio). Even if 1,4-cyclohexanedimethanol exceeds 10 moles, no further improvement in the effect can be expected, and the degree of crystallinity also increases, which tends to reduce adhesion. It is unsuitable because the improvement in adhesive performance is small.
Glycols other than 1,4-cyclohexanedimethanol must have a molecular weight of 300 or less. When using a material with a molecular weight exceeding 300, there is a tendency for adhesiveness to decrease.
Although unsuitable for the polyester resin of the present invention,
However, it is preferable to use a small amount of polytetramethylene ether glycol having a molecular weight of 500 to 1000, since this improves adhesiveness. As the above-mentioned glycol with a molecular weight of 300 or less,
Examples include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, neopentyl glycol, and the like. In addition to being composed of the acid component (A) and the glycol component (B), the polyester resin in the present invention has an intrinsic viscosity (phenol: ethane tetrachloride = 6:
4 (weight ratio) measured at 30℃ in a mixed solvent of
A range of 0.4 to 2.0 is appropriate. If it is less than 0.4, the adhesive strength tends to decrease, and if it exceeds 2.0, the melt viscosity becomes too high and is unsuitable for use. The appropriate melting point is in the range of 40 to 140°C; anything below 40°C will result in a resin with low adhesive strength, and anything over 140°C will be difficult to bond to vinyl chloride resin molded products, other base materials, and vinyl chloride resin molded products. This is not appropriate because the heat deformation of the vinyl chloride resin molded product itself becomes large during heat bonding. Furthermore, the polyester resin used in the present invention is put to practical use in the form of powder, film, fiber, etc., but sticky ones may cause blocking.
It is unsuitable for handling and storage, and if it has no tackiness, it has poor adhesion, so the degree of crystallinity is approximately 5-20% (according to X-ray diffraction).
Those having crystallinity within this range are suitable in terms of handling and adhesive performance. As mentioned above, the polyester resin adhesive of the present invention is suitable as a hot melt type adhesive, but it can also be used as a solvent type adhesive.
In this case, a solution of benzene, toluene, xylene, acetone, ethyl acetate, butyl acetate, dioxane, tetrahydrofuran, cyclohexanone, methyl ethyl ketone, phenol, etc. alone or in a mixture thereof is used. To manufacture the resin, glycol is charged at a ratio of 1.5 to 3 moles per mole of dicarboxylic acid, together with a catalyst and a stabilizer, into a reaction vessel equipped with a stirrer, a total condenser, a partial condenser, and a torque meter, and the temperature is set at 170°C. Carry out the reaction at ~230°C. When the esterification reaction rate has progressed to about 90%, it is effective to apply a vacuum of 200 torr to the reaction system, and when the esterification reaction rate reaches about 97% or more, increase the vacuum to an even higher level.
Lower the reaction temperature to 240 to 260 at the same time as below 1.0 torr.
℃, and use the torque on the torque meter as a guide so that the intrinsic viscosity of the reaction product is 0.4 or more. The present invention particularly relates to molded products of vinyl chloride resin such as sheets, films, leather, foams, etc., or together with these, wood, metal plates, paper, etc.
Used to bond leather, plastic sheets, plastic foam, etc. When using as a hot melt type, an appropriate amount of the polyester resin of the present invention (powder, film, fibrous type) is set between objects to be adhered, and heated and pressurized to a temperature sufficient to melt the polyester resin, or It is also possible to melt the polyester resin and coat it on a base material, and then layer the base material on top of it, using various commercially available applicators, and various methods may be adopted depending on the purpose. Ru. Next, the present invention will be specifically explained with reference to Examples. In the examples, "parts" are "parts by weight" unless otherwise specified. Production example of polyester resin (a) Terephthalic acid 219.3 parts, adipic acid 128.6 parts,
277.5 parts of 1,4-butanediol, 105.0 parts of diethylene glycol, 47.5 parts of 1,4-cyclohexanedimethanol, and 0.3 parts of tetrabutyl titanate.
140~
React at 220°C, then 0.3 parts of antimony trioxide,
Add 0.25 parts of phosphoric acid and react under reduced pressure of 1 torr or less at 250℃, intrinsic viscosity 0.87, melting point 94℃, viscosity 2230 poise (Koka type flow tester 190℃ x 30Kg/cm ² )
of resin was obtained. Production example of polyester resin (b) Adipic acid 212.8 parts, terephthalic acid 241.9 parts,
The reaction was carried out in the same manner as above except that 420 parts of 1,4-butanediol, 54.2 parts of ethylene glycol, and 41.9 parts of 1,4-cyclohexanedimethanol were used, and a resin with an intrinsic viscosity of 0.85, a melting point of 99°C, and a viscosity of 3200 poise was obtained. Obtained. Production example of polyester resin (c) Terephthalic acid 235.0 parts, adipic acid 252.0 parts,
The reaction was carried out in the same manner as above except that 396.0 parts of 1,4-butanediol and 117.0 parts of diethylene glycol were used to obtain a polyester resin having an intrinsic viscosity of 0.83, a melting point of 103° C., and a viscosity of 1820 poise. Production example of polyester resin (d) Terephthalic acid 141.9 parts, adipic acid 124.9 parts,
118.1 parts of 1,4-cyclohexanedimethanol,
The reaction was carried out in the same manner as above except that 615.1 parts of polyethylene glycol (molecular weight 500) was used, and the intrinsic viscosity
1.12, a melting point of 68°C, and a viscosity of 1810 poise. Example 1 A polyester resin (A) was melt-coated to a thickness of 10μ on a vinyl chloride resin film (thickness 50μ), and the vinyl chloride resin film was layered on top of the melt-coated polyester resin (A) to a thickness of 115μ.
After heat sealing at ℃ for 5 seconds, a T-peel peel test was performed and the adhesive strength was 3.5 (Kg/cm).
It was hot. Note that when vinyl chloride resin films were heat-sealed together at 115° C. for 5 seconds without using polyester resin (a), the films did not adhere to each other at all. Also, vinyl chloride resin film and Tetron
100% jersey from the cloth surface at 150℃ x 0.35Kg/cm x 10
When pressed in seconds, the adhesive strength was 2.6 (Kg/25mm). Example 2 Adhesive strength was measured in the same manner as in Example 1 except that polyester resin (b) was used. The results are listed in Table 1. Control Examples 1 to 2 Control example 1 uses polyester resin (c).
The case where polyester resin (d) was used was referred to as Control Example 2, and the adhesive strength was determined in the same manner as in Example 1 and is listed in Table 1. Example 3 Using polyester resin (A), ABS sheets and polycarbonate and vinyl chloride resin film were adhered in the same manner as in Example 1, and the adhesive strength was determined to be 3.2 (Kg/cm) and 3.8 (Kg), respectively. /25mm). Example 4 The adhesive strength was determined in the same manner as in Example 3 except that polyester resin (B) was used, and each was found to be 4.6 (Kg/
cm) and 5.2 (Kg/cm). Control Examples 3 to 4 Control example 3 uses polyester resin (c).
Control example 4 is the case where polyester resin (d) is used, and the adhesive strength was determined in the same manner as in Example 3, and the results were 1.2 (Kg/cm), 1.5 (Kg/25mm), and 0.8 (Kg/cm), respectively.
,
It was 0.7 (Kg/25mm). 【table】

Claims (1)

[Claims] 1 Aromatic dicarboxylic acid and adipic acid as acid components
As (A), 10:90~
A polyester resin adhesive for vinyl chloride resin moldings, which is made of a low-crystalline polyester resin that contains glycol as the glycol component (B) in a ratio of 1:99 (molar ratio), has an intrinsic viscosity of 0.4 to 2.0, and a melting point of 40 to 140°C. agent.