KR100614587B1 - Composition of thermoplastic elastomer resin with a good adhesive property - Google Patents

Abstract

The present invention is a composition comprising a polyether ester elastomer, a styrene-ethylene-butylene-styrene block copolymer, and an inorganic material, wherein the polycarbonate, polybutylene terephthalate, acrylonitrile-butadiene- Excellent adhesiveness during double injection into a composite comprising each of styrene or a composition thereof. When the elastomer composition of the present invention is double-injected into the above composition having a hard surface, the surface hardness is low, matte, and exhibits excellent thermoplastic elastomer performance without slipping.

Adhesive, Polyether Ester Elastomer, Styrene-Ethylene-Butylene-Styrene Block Copolymer

Description

Composition of thermoplastic elastomer resin with excellent adhesive property

The present invention relates to a thermoplastic elastomer resin composition having excellent dual injection properties, and more particularly, to a polyether ester elastomer, a styrene-ethylene-butylene-styrene block copolymer, and an inorganic material. In the case of double injection, the present invention relates to a thermoplastic elastomer resin composition having excellent adhesion to the adherend, low surface hardness, matteness, and no slip.

The thermoplastic elastomer resin composition excellent in adhesiveness according to the present invention is double-injected onto the surface of the structure (adhered body) used in daily life to cover the hard surface of the structure, to prevent slippage by sweat, or contact with a hard mechanism It can improve the physical feel to the part. Structures to which the composition of the present invention can be applied include, but are not limited to, electronic and sporting and leisure items such as tape measures, mobile phones, PDA phones, earphones, or remote controls, which are frequently in contact with hands in daily life. Do not.

In case of using only styrene-ethylene-butylene-styrene block copolymer among the existing materials used for double injection, the Shore Hardness is 10 ~ 30D and the surface hardness is low, matte, and there is no slip, but double injection It does not have good surface adhesiveness with each of polycarbonate, polybutylene terephthalate, acrylonitrile-butadiene-styrene, or a composition thereof, which is a target object, and has a problem of being easily peeled from the adherend during actual use. .

In addition, when only polyether ester elastomer is used, the surface adhesion with the object to be double-injected is excellent, but since the hardness is high in practical use, it is hard, glossy, and there is a need for improvement.

The inventors of the present invention, in order to improve the above-mentioned conventional problems, while maintaining the properties of the elastic body of the existing thermoplastic elastomer, the new thermoplastic elastomer resin improved the adhesion and surface properties with the adherend through the mixing of the composition As a result of repeated studies on the composition, the present invention has been completed.

Therefore, the present invention improves the disadvantage that the styrene-based elastomer has a good surface property for grip in the surface properties of the molded article, while the adhesion with the adherend is poor, and the performance of the elastomer possessed by the thermoplastic elastomer It is an object of the present invention to provide a resin composition having excellent adhesion and surface properties, which is maintained as it is.

The present invention provides an adhesive comprising a polyether ester elastomer (PTEE), a styrene-ethylene-butylene-styrene block copolymer (Styrene-ethylene-buthylene-styrene (SEBS), and an inorganic material. It relates to an elastomer composition having excellent properties and surface properties.

The polyether ester elastomers of the present invention consist of hard segments composed of short chain polyesters and soft segments composed of long chain polyesters. The hard segment consists of an aromatic dicarboxylic acid and a short chain diol component, and the soft segment consists of an aromatic dicarboxylic acid and a polyalkylene oxide component. In other words, the polyether ester elastomer is synthesized from the following three raw materials. It consists of the copolymer of the aromatic dicarboxylic acid component selected from aromatic dicarboxylic acid and its ester forming derivative, the group which consists of aliphatic diol of C2-C10, and the long chain diol component which is polyalkylene oxide.

Aromatic dicarboxylic acids that can be used in the present invention are terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, or 4,4 ' Diphenoxyethanedicarboxylic acids, ester forming derivatives of aromatic dicarboxylic acids include dimethyl terephthalate, dimethyl isophthalate, dimethyl phthalate, diethyl terephthalate, diethylisophthalate, diethyl phthalate, di- n-propyl terephthalate, di-n-propyl isophthalate, isopropyl terephthalate, di-t-butyl terephthalate, butylbenzyl terephthalate, diethyl 2,6-naphthalene-dicarboxylate, diethyl 2,7 -Naphthalenedicarboxylate, or dimethyl diphenyl-4,4'-dicarboxylate. In the present invention, the di-acid may be used alone or in combination of the dicarboxylic acid and its ester-forming derivatives. Among the compounds usable as the above components, it is preferable to use at least one selected from the group consisting of terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, and dimethyl terephthalate.

As the di-ol component of the polyether ester elastomer of the present invention, one or more diols selected from the group consisting of aliphatic diols having 2 to 10 carbon atoms can be used. Preferably one or more selected from the group consisting of ethylene glycol, 1,3-propylenediol, 1,4-butanediol, pentamethylene glycol, hexamethylene glycol and 1,4-cyclohexanedimethanol can be used, more preferably 1,4-butanediol can be used.

Polyalkylene oxide (Polyalkylene Oxide) that can be used in the present invention can be used polyoxyethylene glycol (Polyoxyethylene glycol), polyoxypropylene glycol (Polyoxypropylene glycol), or polyoxytetramethylene glycol (PTMG) have. Among them, the use of PTMG is preferred. When the long chain diol component PTMG is used, the polyether ester elastomer exhibits excellent elasticity and elastic recovery, low permanent compressive strain and low temperature impact strength. The PTMG used in the present invention is preferably 60 to 80% by weight based on the weight of the polyether ester elastomer. If the PTMG content is less than 60% by weight, the hardness of the composition of the present invention becomes high, and if it exceeds 80% by weight, there is a processing problem.

Generally, the hard segments of polyether ester elastomers consist of short chain esters, and the soft segments of polyether ester elastomers consist of long chain esters. The ends of the polyether portions of the long chain esters are linked to the dicarboxylic acids via ester linkages so that the soft and hard segments are linked to each other. Soft segments in the present invention have been defined as comprising ester linkages at the ends of their polyether moieties. Specifically, the polyether ester elastomer is composed of a hard segment composed of polybutylene terephthalate and a soft segment composed of polyoxytetramethylene glycol (PTMG).

It is preferable to use 35-45 weight% of the polyether ester elastomer used by this invention with respect to the resin composition of this invention. If the weight of the polyether ester elastomer is less than 35% by weight, the adhesion is inferior, and if it exceeds 45% by weight, it is difficult to obtain desired surface properties.

The thermoplastic resin composition according to the present invention uses styrene-ethylene-butylene-styrene block copolymer as a surface improving agent. It is a rubber component, which greatly improves weather resistance and durability of existing styrene-butadiene-styrene (SBS), and is made of a polar molecule such as styrene, and is easily mixed with polyether ester. The styrene-ethylene-butylene-styrene block copolymer that can be used in the present invention has a styrene content of 20 to 50% by weight relative to the block copolymer, and an content of ethylene / butylene copolymer block (EB) is 50 to 80% by weight. It is preferable that it is%. If the styrene content in the SEBS is less than 20% by weight, the ethylene / butylene content of the styrene-ethylene-butylene-styrene is increased to lose weather resistance, heat resistance and surface properties, and if the styrene content exceeds 50% by weight, Rubber properties are lost and hardness is increased. In addition, when the content of the ethylene / butylene copolymer block (EB) is less than 50% by weight, the hardness becomes high, and when it exceeds 80% by weight, weather resistance and heat resistance are lost.

When the styrene-ethylene-butylene-styrene block copolymer is used in an amount of more than 55% by weight as the surface modifier, 45 to 55% by weight is used in the resin composition because the adhesiveness with the adherend is lowered during the double injection desired in the present invention. It is desirable to. When the amount of use is less than 45% by weight, in double injection, the adhesiveness is increased by the polyether ester elastomer component, but two of the surface properties such as adhesion with the adherend to be obtained in the present invention and surface slip or hardness A problem arises in which all the properties cannot be obtained. In other words, the adhesion is improved, but the surface properties are lost.

The inorganic material that can be used as an additive in the composition of the present invention may be used at least one selected from the group consisting of calcium carbonate, antimony trioxide (Sb ₂ O ₃ ), mica, talc, and clay. The inorganic material is preferably used in 2 to 10% by weight based on the composition of the present invention. When the inorganic substance exceeds 10% by weight, the adhesion to the adherend and the hardness are improved, resulting in poor surface feel. When the amount of the inorganic substance used is less than 2% by weight, it is not preferable because the effect of the non-slip of the surface of the object is insufficient.

Other compositions of the present invention may further comprise a pigment. As the pigment which can be used in the composition of the present invention, carbon black, titanium oxide, zinc oxide, azo pigment, nitro pigment or lake pigment can be used. The usage-amount can be used up to 4.0 weight% in a resin composition in the quantity normally used. Use above 4.0% by weight results in an increase in hardness.

The melt blend temperature of these compositions may be any temperature at which these components can be melted, but is generally 190 to 230 ° C, preferably 200 to 220 ° C. An extrudate is inject | poured after drying at 100 degreeC for 2 hours.

Hereinafter, the present invention will be described in detail by the following examples. However, these examples and test examples are only for the understanding of the present invention, and the present invention is not limited thereto.

Examples 1-5

Styrene-ethylene-butylene-styrene block copolymer (Dynasol, 6120 Grade, styrene content 30 wt%) based on polyether ester elastomer (Samyang, TRIEL 5300NA, specific gravity 1.110 (23 ℃), melt index 31g / 10min) %, Ethylene / butylene copolymer block content of 70% by weight) and calcium carbonate (OMYA, 1 Grade) was blended in the ratio as shown in Table 1 in a twin screw compressor (ZSK 25). After mixing the composition, the compressor temperature was melt kneaded at 210 ° C. to prepare a thermoplastic elastomer resin composition.

The physical properties of the thermoplastic elastomer according to the present invention were confirmed by measuring the following items.

1. Adhesive with adherend

A molder for forming an adherend having a length of 60 mm, a width of 13 mm, and a thickness of 3 mm and a molded product having a length of 60 mm, a width of 13 mm, and a thickness of 6 mm was prepared. First, an adherend molded article having a thickness of 3 mm was made, and then an adherend was inserted into a mold capable of making a molded article having a thickness of 6 mm. Then, the resin composition of the present invention was injected to make a double injection molded product. In injection | pouring, the to-be-inserted object was inserted in the normal temperature state, and mold temperature was also made into the normal temperature state. The cylinder temperature of the injection molding machine was 210 degreeC, and cooling time was 20 second.

The adhesion test with the adherend of the double injection molding was determined as follows based on the load of 7 kg _f .

O: Adhesion is maintained for 10 seconds or more at 7 kg _f .

X: separated from the adherend in less than 10 seconds at 7 kg _f .

2. Hardness measurement

Hardness was measured for Shore D by ASTM D2240.

3. Surface Characteristics

When touching the surface by hand, the degree of slip was measured and classified as follows.

O: no surface slip

△: slight surface slip

X: With surface slip

4.surface polished

Visually, it was classified as follows.

O: Gloss on the surface

X: No gloss on the surface

These measurement results are shown in Tables 1 and 2.

Comparative example

The same materials and equipment as in Example were used, except that the composition was melt kneaded in the composition shown in Table 2 to prepare a thermoplastic elastomer resin composition.

division Example 1 Example 2 Example 3 Example 4 Example 5 Furtherance TPEE 40 35 45 40 44 SEBS 50 55 45 50 54 Mineral Calcium carbonate 10 10 10 - - Mica - - - 10 2 Adherend and adhesiveness PC O O O O O ABS O O O O O PBT O O O O O Hardness Shore d 30 28 32 30 31 Polish - X X X X X slide - O O O O O * TPE: polyether ester elastomer * SEBS: styrene-ethylene-butylene-styrene block copolymer * PC: polycarbonate * ABS: acrylonitrile butadiene styrene * PBT: polybutylene terephthalate

division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4                                              Furtherance TPEE 30 50 35 50 SEBS 60 40 45 40 Mineral Calcium carbonate 10 10 20 - Mica - - - 10 Adherend and adhesiveness PC X O X O ABS X O X O PBT X O X O Hardness Shore d 26 32 35 32 Polish - X O X O slide - X △ △ △

From the results of Table 1 and Table 2, the thermoplastic elastomer obtained from the present invention has excellent surface adhesion with the adherend in double injection, and shows excellent surface properties without slip when the surface of the injection molded product is in contact with the hand. It can be seen.

The thermoplastic elastomer composition according to the present invention has good dual injection property and low hardness, matteness and non-slip surface property with good adhesion to the adherend. The composition according to the present invention is also basically composed of a material having excellent weather resistance and heat resistance, so that it can be used for a long time, and when used in a low temperature climate, the shock absorbing effect on the structure is prevented, and the product is not destroyed, and it is directly contacted with the hand. It prevents heat loss.

Claims (8)

About the resin composition 35 to 45 weight percent polyether ester elastomer comprising 60 to 80 weight percent polyoxytetramethylene glycol in soft segment; 45 to 55% by weight of styrene-ethylene-butylene-styrene block copolymer; And 2 to 10 wt% mineral Including, A thermoplastic elastomer composition, wherein the thermoplastic elastomer composition is adhered to at least one adhesive selected from the group consisting of polycarbonate, polybutylene terephthalate, and acrylonitrile-butadiene-styrene. delete delete The method of claim 1, wherein the hard segment of the polyether ester elastomer is at least one dicarboxylic acid or ester formed thereof selected from the group consisting of terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid and dimethyl terephthalate. Elastomer composition comprising a derivative. The polyether ester elastomer according to claim 1, wherein the polyether ester elastomer is one selected from the group consisting of ethylene glycol, 1,3-propylenediol, 1,4-butanediol, pentamethylene glycol, hexamethylene glycol and 1,4-cyclohexanedimethanol An elastomer composition comprising the above diol component. The styrene-ethylene-butylene-styrene block copolymer according to claim 1, wherein the styrene-ethylene-butylene-styrene block copolymer has a styrene content of 20 to 50% by weight relative to the styrene-ethylene-butylene-styrene block copolymer and a content of ethylene / butylene copolymer block. Elastomer composition, characterized in that 50 to 80% by weight relative to the silver styrene-ethylene-butylene-styrene block copolymer. The elastomer composition according to claim 1, wherein the inorganic material is at least one selected from the group consisting of calcium carbonate, antimony trioxide (Sb ₂ O ₃ ), mica, talc, and clay. The ilesto of claim 1, further comprising a pigment selected from the group consisting of carbon black, titanium oxide, zinc oxide, azo pigments, nitro pigments, and lake pigments in an amount of 4.0% by weight or less relative to the resin composition. MER composition.