JP3464537B2 - Polymer composition - Google Patents

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention has an excellent mechanical balance of rigidity, strength, impact resilience, etc., and can be melt-molded at low temperature, and has moldability, adhesiveness and hydrolysis resistance. ,
The present invention relates to a polymer composition having excellent oil resistance.

[0002]

2. Description of the Related Art A caprolactone polymer has a melting point near 60 ° C. and has a property of crystallizing and solidifying by heating and melting and then cooling, and therefore, hot water heating processing and the like are possible. The resin composition thus heat-processed has an excellent balance of mechanical properties such as hardness, strength and elongation. Utilizing such characteristics, it is known to be used as a cast material for medical use, auxiliary wood, golf ball cover material, various molding materials, and hot melt adhesive.

[0003]

Although the caprolactone polymer has the above-mentioned excellent properties, it has been desired to impart flexibility because it has too high rigidity depending on the application. Also, in the application as a hot melt adhesive,
Adhesive strength to metals such as iron and aluminum and certain resin materials such as polyethylene terephthalate film is not sufficient, and its use as an adhesive is limited. further,
The caprolactone polymer has a problem that it is easily hydrolyzed.

The present invention has improved the above-mentioned drawbacks, is capable of low-temperature molding, has an excellent balance of mechanical properties such as rigidity and strength, and can be melt-molded at low temperature. And a polymer composition having excellent adhesiveness, oil resistance, and hydrolysis resistance.

[0005]

Means for Solving the Problems As a result of intensive investigations by the present inventors in order to improve the above-mentioned drawbacks of the caprolactone polymer, a caprolactone polymer having a specified number average molecular weight (Mn) and an epoxy-modified polymer were obtained. A polymer composition containing a block copolymer in a specific composition range solves these problems all at once, has an excellent balance of mechanical properties such as rigidity and strength, and can be melt-molded at low temperature. Therefore, they have found that they have excellent moldability and moldability, adhesiveness, and hydrolysis resistance, and have reached the present invention.

That is, according to the present invention, (a) 5 to 90% by weight of a caprolactone polymer having a number average molecular weight of 1,000 to 200,000, and (b) a polymer block of an aromatic vinyl compound in the same molecule. Conjugated diene compound polymer block in which epoxy is partially added and /
Or, an epoxy-modified block copolymer consisting of a hydrogenated conjugated diene compound polymer block partially added with epoxy is contained in an amount of 95 to 10% by weight (the total of (a) and (b) is 100% by weight). A polymer composition is provided. Further, according to the present invention, there is provided the polymer composition in which the number average molecular weight of the caprolactone polymer is in the range of 5,000 to 150,000. Hereinafter, the present invention will be described in detail.

The number average molecular weight of the caprolactone polymer which is the component (a) constituting the polymer composition of the present invention is 1,0.
It is indispensable to be in the range of 00 to 200,000, preferably in the range of 5,000 to 150,000, and particularly preferably in the range of 10,000 to 150,000. When the number average molecular weight is lower than the essential range, the resulting polymer composition does not have sufficient strength and rigidity, and when the number is higher than the range of the number average molecular weight, it is molded by molding. Properties deteriorate and processing becomes difficult. Examples of the caprolactone polymer having the above-specified number average molecular weight range in the present invention include Placcel H-1 and Placcel H- manufactured by Daicel Chemical Industries, Ltd.
4, Placcel H-7 and the like.

The epoxy-modified block copolymer, which is the component (b) which constitutes the polymer composition of the present invention, is a conjugate in which epoxy is partially added to the polymer block of the aromatic vinyl compound in the same molecule. It is a diene compound polymer block or a hydrogenated conjugated diene compound polymer block to which epoxy is partially added. The former is one in which epoxy is added to the block copolymer of aromatic vinyl compound and conjugated diene compound, and the latter is the one in which epoxy is also added to the partial hydride of the block copolymer of aromatic vinyl compound and conjugated diene compound. It was done. Examples of the aromatic vinyl compound constituting the block copolymer include styrene alone or, together with styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, vinylxylene, ethylvinylxylene, vinylnaphthalene and the like. . As the conjugated diene compound, each of butadiene and isoprene, or butadiene (when isoprene is the main component), isoprene (when butadiene is the main component), 1,3-pentadiene, and 2,3-dimethyl are added to them. Examples are conjugated dienes such as butadiene. The block copolymer has various structures, and examples thereof include those having an aromatic vinyl compound block at the terminal, particularly preferably a styrene block. The number average molecular weight of the block copolymer is preferably about 10,0.
00 to about 1,000,000, especially about 20,000 to
It is preferably in the range of 300,000.

The hydride of the block copolymer is preferably one in which 0 to 99% of the aliphatic double bonds are hydrogenated.

The epoxy-modified block copolymer of the present invention is a block copolymer or hydrogenated block copolymer to which epoxy is added. Epoxy is added with peracetic acid, formic acid, perbenzoic acid, trifluoroperacetic acid, etc., and the epoxy equivalent of the epoxy modified block copolymer obtained is usually 150 to 10,000.
The range is 0, preferably 200 to 6,000.

The composition ratio of the caprolactone polymer and the epoxy-modified block copolymer is 5 for the caprolactone polymer.
To 90% by weight, the epoxy-modified block copolymer is 95 to 10% by weight, preferably the caprolactone polymer is 10 to 80% by weight, the epoxy-modified block copolymer is 90 to 20% by weight. (The total of both is 100% by weight). When the composition ratio of the caprolactone polymer is less than 5% by weight, the mechanical properties such as rigidity and strength of the composition are not sufficient, and when it exceeds 90% by weight, the flexibility of the composition becomes small and the adhesive property is low. The improvement effect of is not sufficient.

In the composition of the present invention, it is essential to use an epoxy-modified block copolymer and a caprolactone polymer, but depending on the use, a tackifier resin, a plasticizer and an inorganic filler may be further added. You can Furthermore, stabilizers, pigments and the like, which are general additives for thermoplastic polymers, can be appropriately added to the composition of the present invention.

The amount of the tackifier resin used is usually 100 parts by weight in total of (a) caprolactone polymer and (b) epoxy-modified block copolymer (hereinafter, both are also referred to as "both polymers"). It is in the range of 1 to 30 parts by weight. Examples of the tackifier resin include rosin acid, hydrogenated rosin acid, maleated rosin acid, ester gum, ester gum H, polyterpene resin, C ₅ petroleum resin, styrene resin, alkylphenol resin, terpene phenol resin and the like. Can be mentioned.

The amount of the plasticizer used is usually in the range of 1 to 30 parts by weight per 100 parts by weight of both polymers. Examples of the plasticizer include dibutyl phthalate, di (2-ethylhexyl) phthalate, di (2-ethylhexyl) adipate, diethylene glycol dibenzoate, butyl stearate, butyl epoxy stearate, and tri (2-ethylhexyl) phosphate. .

The amount of the inorganic filler used is usually in the range of 1 to 100 parts by weight based on 100 parts by weight of both polymers. Examples of inorganic fillers include calcium carbonate, silicic acid,
Examples thereof include calcium silicate, clay, talc, mica and bentonite.

The amount of the stabilizer used is usually in the range of 0.01 to 5 parts by weight per 100 parts by weight of both polymers, and the amount of the pigment used is 0 per 100 parts by weight of both polymers. The range is from 1 to 20 parts by weight.

The polymer composition of the present invention can be easily produced by mixing the respective components by a kneading machine such as an extractor or a kneader roll. The setting temperature of these kneading devices can be freely selected within the range of 60 to 200 ° C,
It is preferable to set in the range of 180 ° C.

As another mixing method, both polymers may be dissolved in a suitable solvent and mixed in a solution.
Examples of preferable solvents include benzene, toluene, carbon tetrachloride, tetrahydrofuran, trichloroethylene, chlorobenzene, chloroform and the like.

The composition of the present invention can be crosslinked, if necessary, with an ordinary curing agent used for the epoxy resin composition. For example, amines, acid anhydrides,
Crosslinking with polymercaptan, phenolic resin, etc. can be performed.

If desired, the composition of the present invention can be vulcanized by a conventional vulcanization method used for the conjugated diene polymer composition. For example, a chemical vulcanizing method using a sulfur compound vulcanizing agent system, a thiuram compound vulcanizing agent system, a peroxide compound vulcanizing agent, or the like can be used, or a physical vulcanizing method such as electron beam irradiation can be used. You can also By performing such vulcanization,
The impact resilience and oil resistance of the composition can be improved.

[0021]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples.

The (a) caprolactone polymer, (b) epoxy modified block copolymer and (hydrogenated) block copolymer used in the examples and comparative examples of the present invention are as follows. Praxel H-7 (manufactured by Daicel Chemical Industries, Ltd.): M
n7-100,000 caprolactone polymers. Epoxy-modified block copolymer (A): Styrene / butadiene weight ratio = 30/70 30% butadiene block of styrene-butadiene-styrene block copolymer
The hydrogenated product was epoxidized with peracetic acid (epoxy equivalent 283). Epoxy-modified block copolymer (B): Tuftec H1
041 (styrene block / rubber (conjugated diene block) weight ratio = 30/70: manufactured by Asahi Kasei Corporation) was epoxidized with peracetic acid (epoxy equivalent 573).
0). Epoxy-modified block copolymer (C): TR2000
(Styrene-butadiene-styrene block copolymer having a styrene / butadiene weight ratio of 40/60: manufactured by Nippon Synthetic Rubber Co., Ltd.) was epoxidized using peracetic acid (epoxy equivalent 508). Epoxy-modified block copolymer (D): Califlex TR1111 (styrene / isoprene weight ratio = 21/7
The styrene-isoprene-styrene block copolymer of 9: manufactured by Shell Chemical Co., Ltd. was epoxidized with peracetic acid (epoxy equivalent 520).

(Examples 1 to 5, Comparative Examples 1 and 2) A caprolactone polymer (manufactured by Daicel Chemical Industries, Ltd., Praxel H-7) and an epoxy block copolymer (hereinafter, simply referred to as an unmodified block copolymer) (Also referred to as "block copolymer") was weighed in a total amount of 50 g at the composition ratio shown in Table-1, thoroughly stirred, and then put into a Labo Plastomill (manufactured by Toyo Seiki Seisakusho Co., Ltd.) set at 140 ° C, and screwed. Kneading was carried out for 5 minutes at a rotation speed of 50 rpm to obtain a polymer composition. The obtained composition was press-molded at 150 ° C. to obtain each test piece sample. The results of the physical property test are shown in Table 1. Although the physical properties of the composition change depending on the composition of the polymer component, the composition having excellent balance of hardness, tensile strength, mechanical properties such as impact resilience, oil resistance, and good adhesion is within the composition range of the present invention. I know there is.

[0024]

[Table 1]

(Examples 6 to 9 and Comparative Examples 3 to 5) 30 g of a block copolymer having various structures shown in Table 2 and 20 g of a caprolactone polymer (Placcel H-7, manufactured by Daicel Chemical Industries Ltd.) were used. Weigh and knead as in Example 1,
The physical properties were tested. The results are shown in Table-2. The physical properties vary depending on the type of epoxy-modified block copolymer,
It is a composition having an excellent balance of mechanical properties such as hardness, tensile strength and impact resilience, good adhesiveness and oil resistance, and excellent processability such as softening temperature and moldability.

[0026]

[Table 2]

(Example 10, Comparative Example 6) 30 g of the epoxy-modified block copolymer (C) and 20 g of the caprolactone polymer having the number average molecular weight shown in Table 3 were weighed and kneaded in the same manner as in Example 1 to obtain the physical properties. Was tested. The results are shown in Table-3.
It can be seen that the physical properties of the composition change depending on the molecular weight of the caprolactone polymer, and the impact resilience significantly decreases when the molecular weight is 1,000 or less.

[0028]

[Table 3]

(Example 11 and Comparative Example 7) 5 g of the block copolymer and 45 g of caprolactone polymer (Placcel H-7, manufactured by Daicel Chemical Industries, Ltd.) were weighed, and Example 1
The mixture was kneaded in the same manner as above, the test piece was stored in water at 50 ° C. for 1 month, and the physical properties were measured. The results are shown in Table-4. It can be seen that in the case of the epoxy-modified block copolymer, the hydrolysis resistance is improved.

[0030]

[Table 4]

Example 12 18.2 g of epoxy modified block copolymer (C), caprolactone polymer (Placcel H-7, manufactured by Daicel Chemical Industries, Ltd.) 12.1.
g, 4.5 g of rosin acid and 15.2 g of mica were weighed and kneaded in the same manner as in Example 1 to measure physical properties. As a result, the tensile strength () was 450 kg / cm ² , the adhesive strength (, SUS) was 48 kg / cm ² , and the adhesive strength (, P
ET film) was 780 g / cm, and oil resistance was 10%.

[0032]

The composition of the present invention is excellent in balance of mechanical properties such as hardness and tensile strength, and also excellent in oil resistance and adhesiveness. Taking advantage of these characteristics, medical cast materials, secondary wood, golf ball cover materials, various mold materials,
It can be used as a hot melt adhesive.

─────────────────────────────────────────────────── --Continued from the front page (56) Reference JP-A 61-42679 (JP, A) JP-A 2-60672 (JP, A) JP-A 2-60642 (JP, A) JP-A 62- 50043 (JP, A) JP 60-130102 (JP, A) JP 60-60974 (JP, A) JP 60-28585 (JP, A) JP 59-96160 (JP, A) JP-A-57-200450 (JP, A) JP-A-57-137351 (JP, A) JP-A-6-220124 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 63/00-63/10 C08L 53/02 C08L 67/04

Claims (2)

(57) [Claims] 1. (a) The number average molecular weight is 1,000 to 20.
5 to 90% by weight of a caprolactone polymer of 50,000, and (b) a polymer block of an aromatic vinyl compound and a conjugated diene compound polymer block and / or partial epoxy partially added in the same molecule Epoxy-modified block copolymer 95 to 10 comprising a hydrogenated conjugated diene compound polymer block in which epoxy is added to
A polymer composition comprising 100% by weight (the total of (a) and (b) is 100% by weight). 2. The polymer composition according to claim 1, wherein the number average molecular weight of (a) the caprolactone polymer is in the range of 5,000 to 150,000.