Resin composition

Abstract

To provide a resin composition capable of suppressing lowering tensile breaking stress.SOLUTION: A resin composition contains a polar main material resin other than a liquid crystal polymer, a low melting point liquid crystal polymer having a crystal meting temperature of 250°C or lower, and an acid-modified polyolefin resin, wherein the polar main material resin constitutes a sea part, and each of the low melting point liquid crystal polymer and the acid-modified polyolefin resin constitutes an island part.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a resin composition.

Background Art

[0002] Among polyester resins, liquid crystal polymers have good hydrolysis resistance. However, it is difficult to knead a liquid crystal polymer with a crystal melting temperature of 280°C or higher with other resins to form a polymer alloy. Therefore, a resin composition in which a low melting point liquid crystal polymer with a crystal melting temperature of 250°C or lower is polymer alloyed with other resins is commercially available (see, for example, Patent Documents 1 and 2).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] In a resin composition in which a low melting point liquid crystal polymer with a crystal melting temperature of 250°C or lower is finely dispersed, the hydrolysis resistance of the liquid crystal polymer is affected and decreases. When stored or used under humid conditions, there is a problem that the tensile fracture stress of the resin composition decreases.

[0005] The present invention has been made in view of the above circumstances, and an object thereof is to provide a resin composition capable of suppressing a decrease in tensile fracture stress.

Means for Solving the Problems

[0006] The first aspect is a resin composition containing a polar main material resin other than a liquid crystal polymer, a low melting point liquid crystal polymer having a crystal melting temperature of 250°C or lower, and an acid-modified polyolefin resin, wherein the polar main material resin constitutes a sea portion, and the low melting point liquid crystal polymer and the acid-modified polyolefin resin each constitute an island portion to form a sea-island structure.

[0007] The second aspect is, in the first aspect, the polar main material resin is at least one selected from the group consisting of a resin having a hydrocarbon chain as the main chain and having a chlorine atom, an oxygen atom or a nitrogen atom other than the main chain, a resin having an oxygen atom in the main chain, or a resin having a nitrogen atom in the main chain. The third aspect is, in the first aspect, the polar main material resin is at least one selected from resins having an oxygen atom in the main chain. The fourth aspect is, in the first aspect, the polar main material resin is a polyester resin other than a liquid crystal polymer.

[0008] The fifth aspect is, in any one of the first to third aspects, taking the whole of the resin composition as 100 parts by weight, the polar main material resin is 40 to 60 parts by weight, the low melting point liquid crystal polymer is 20 to 40 parts by weight, and the acid-modified polyolefin resin is 5 to 30 parts by weight.

Advantages of the Invention

[0009] According to the present invention, it is possible to provide a resin composition capable of suppressing a decrease in tensile fracture stress.

Brief Description of the Drawings

[0010]

Figure 1

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Figure 6

Embodiments for Carrying Out the Invention

[0011] Hereinafter, the present invention will be described based on preferred embodiments.

[0012] The resin composition of the embodiment contains a polar main resin other than a liquid crystal polymer, a low melting point liquid crystal polymer having a crystal melting temperature of 250°C or lower, and an acid-modified polyolefin resin.

[0013] In the resin composition of the embodiment, a sea-island structure is formed in which the polar main resin constitutes a sea portion, and the low melting point liquid crystal polymer and the acid-modified polyolefin resin each constitute an island portion.

[0014] Examples of the polar main resin include at least one selected from the group consisting of (1) a resin having a hydrocarbon chain as the main chain and having a chlorine atom, an oxygen atom, or a nitrogen atom outside the main chain, (2) a resin having an oxygen atom in the main chain, and (3) a resin having a nitrogen atom in the main chain. The polar main resin is a resin different from both the low melting point liquid crystal polymer and the acid-modified polyolefin resin.

[0015] Examples of the polar main resin having a hydrocarbon chain as the main chain include a polymer of at least one polar monomer and a copolymer of the polar monomer and an olefin. Examples of the polar monomer include vinyl chloride, vinylidene chloride, vinyl acetate, vinyl alcohol, acrylonitrile, (meth)acrylic acid, (meth)acrylic acid ester, and the like. Examples of the olefin that becomes a monomer of the polar main resin include α-olefins such as ethylene, propylene, 1-butene, 1-hexene, and 1-octene; cyclic olefins such as cyclopentene, cyclohexene, and norbornene; aromatic olefins such as styrene; and dienes such as butadiene and isoprene.

[0016] Specific examples of the polar main component resin whose main chain consists of a hydrocarbon chain are not particularly limited, but include polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyvinyl alcohol, polyacrylonitrile, poly(meth)acrylic acid, poly(meth)acrylate, ethylene-vinyl chloride copolymer, ethylene-vinylidene chloride copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-acrylonitrile copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylate copolymer, acrylonitrile-butadiene copolymer, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-butadiene-(meth)acrylate copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-(meth)acrylate copolymer, and the like.

[0017] Examples of the polar main component resin having an oxygen atom in the main chain include polyester resins, polyether resins, polyether ester resins, polycarbonate resins, polyurethane resins, and the like. Examples of the polar main component resin having a nitrogen atom in the main chain include polyamide resins, polyimide resins, polyamideimide resins, and the like.

[0018] Note that polyetherimide resins, polyurethane resins, etc. are polar main component resins having an oxygen atom and a nitrogen atom in the main chain. The polyurethane resin may have an oxygen atom based on a urethane bond (-NH-CO-O-), or may have an oxygen atom derived from a polyester polyol or a polyether polyol between the urethane bonds.

[0019] The polar main component resin preferably contains a polyester resin other than a liquid crystal polymer. These polyester resins are non-liquid crystal polyester resins, and may be, for example, linear polyester resins obtained by condensation polymerization of a dicarboxylic acid component and a diol component.

[0020] Examples of the dicarboxylic acid component of the polyester resin include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, naphthalene-1,4-dicarboxylic acid, and naphthalene-2,6-dicarboxylic acid, and aliphatic dicarboxylic acids such as adipic acid and sebacic acid. Examples of the diol component of the polyester resin include linear diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexamethylene diol; branched diols such as neopentyl glycol and 2,2-dialkyl-1,3-propanediol; and cyclic diols such as cyclopentanedimethanol and cyclohexanedimethanol. Examples of the alkyl group of the side chain branched from the main chain of the branched diol include methyl group, ethyl group, propyl group, and butyl group.

[0021] Specific examples of the polyester resin are not particularly limited, and include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polytrimethylene terephthalate, and modified polyesters in which part of the dicarboxylic acid component and / or diol component in these polyesters is modified with other dicarboxylic acid components and / or diol components.

[0022] The resin composition contains a low melting point liquid crystal polymer having a crystal melting temperature of 250°C or lower. The liquid crystal polymer is a thermoplastic resin that exhibits liquid crystallinity when melted, and a liquid crystal polymer composed of a polyester resin is preferred. The polar main resin may be a thermoplastic resin that does not exhibit liquid crystallinity when melted.

[0023] The low melting point liquid crystal polymer may be composed of only one type of low melting point liquid crystal polymer, or may be a mixture of multiple types of low melting point liquid crystal polymers. The low melting point liquid crystal polymer may be a liquid crystal polyester or liquid crystal polyester amide that forms an anisotropic molten layer called a thermotropic liquid crystal polymer, and a liquid crystal polyester is preferred.

[0024] The crystal melting temperature of the low melting point liquid crystal polymer is the temperature of the crystal melting peak measured using a differential scanning calorimeter. The measurement method using a differential scanning calorimeter is as follows: after observing the endothermic peak temperature (Tm1) observed when measuring under a temperature rising condition of 20 °C / min from room temperature, it is held at a temperature 20 to 50 °C higher than Tm1 for 10 minutes, and then, after cooling the sample to room temperature under a temperature decreasing condition of 20 °C / min, the endothermic peak is observed again when measuring under a temperature rising condition of 20 °C / min, and the temperature indicating the peak top is taken as the crystal melting temperature of the liquid crystal polymer. The crystal melting temperature of the low melting point liquid crystal polymer is 250 °C or lower, preferably 160 °C to 240 °C, more preferably 170 °C to 230 °C, and particularly preferably 200 °C to 230 °C.

[0025] Examples of the repeating unit constituting the low melting point liquid crystal polymer include an aromatic hydroxycarboxylic acid unit (-O-Ar-CO-), an aromatic dicarboxylic acid unit (-CO-Ar-CO-), an aromatic diol unit (-O-Ar-O-), an aromatic aminocarboxylic acid unit (-NH-Ar-CO-), an aromatic hydroxyamine unit (-O-Ar-NH-), an aromatic diamine unit (-NH-Ar-NH-), an aliphatic diol unit (-O-Ra-O-), and an aliphatic dicarboxylic acid unit (-O-Ra-O-). Here, -Ar- represents an aromatic group, and -Ra- represents an aliphatic group. The -CO- group contained in these units is not limited to being derived from carboxylic acid (-CO-OH), and may be derived from an acyl compound (-CO-O-COR), an ester derivative (-CO-OR), an acid halide (-CO-X), etc. Further, the -O- group and -NH- group are not limited to being derived from a hydroxy group (-OH) and an amino group (-NH2), respectively, and may be derived from an acyl compound (-O-COR and -NH-COR), etc. Here, R represents an organic group such as an alkyl group or an aryl group, and X represents a halogen atom. These repeating units constituting the liquid crystal polymer may be only one kind or a combination of two or more kinds as long as a polyester is formed as the low melting point liquid crystal polymer, but it is desirable to contain at least one kind of hydroxycarboxylic acid unit. As the low melting point liquid crystal polymer, an all-aromatic low melting point liquid crystal polymer in which each repeating unit contains all aromatic groups is preferable.

[0026] Specific examples of the aromatic hydroxycarboxylic acid unit include 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 2-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 5-hydroxy-2-naphthoic acid, 7-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 4'-hydroxyphenyl-4-benzoic acid, 3'-hydroxyphenyl-4-benzoic acid, 4'-hydroxyphenyl-3-benzoic acid, and units derived from their alkyl, alkoxy, or halogen substituents. Among these, from the viewpoint of easily adjusting the heat resistance, mechanical strength, and melting point of the resulting liquid crystal polymer, units derived from one or more selected from the group consisting of 4-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid are preferred.

[0027] Specific examples of the aromatic dicarboxylic acid unit include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4'-dicarboxybiphenyl, 3,4'-dicarboxybiphenyl, and 4,4''-dicarboxytriphenyl, and units derived from their alkyl, alkoxy, or halogen substituents. Among these, from the viewpoint of effectively enhancing the heat resistance of the resulting liquid crystal polymer, units derived from one or more selected from the group consisting of terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid are preferred, and terephthalic acid units or 2,6-naphthalenedicarboxylic acid units are more preferred.

[0028] Specific examples of the aromatic diol units include units derived from hydroquinone, resorcinol, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 3,3'-dihydroxybiphenyl, 3,4'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl ether, and 2,2'-dihydroxybinaphthyl, and their alkyl, alkoxy, or halogen-substituted derivatives. Among these, from the viewpoint of excellent reactivity during polymerization, units derived from one or more selected from the group consisting of hydroquinone, resorcinol, 4,4'-dihydroxybiphenyl, and 2,6-dihydroxynaphthalene are preferred, and units derived from one or more selected from the group consisting of hydroquinone, 4,4'-dihydroxybiphenyl, and 2,6-dihydroxynaphthalene are more preferred.

[0029] Specific examples of the aliphatic diol units include units derived from ethylene glycol, 1,4-butanediol, and 1,6-hexanediol. Also, during production, a polymer containing an aliphatic diol such as polyethylene terephthalate or polybutylene terephthalate may be reacted with the above-mentioned aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, aromatic diol, and their acylates, ester derivatives, acid halides, etc.

[0030] Specific examples of the aliphatic dicarboxylic acid units include units derived from oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, fumaric acid, maleic acid, 1,4-cyclohexanedicarboxylic acid, and hexahydroterephthalic acid. Among these, from the viewpoint of excellent reactivity during polymerization, units derived from oxalic acid, succinic acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid, and 1,4-cyclohexanedicarboxylic acid are preferred.

[0031] The resin composition contains an acid-modified polyolefin resin. Examples of the acid-modified polyolefin resin include an acid-modified polyethylene resin and an acid-modified polypropylene resin. Examples of polyethylene include low-density polyethylene, high-density polyethylene, linear low-density polyethylene, etc. Examples of polypropylene include homopolypropylene, block polypropylene, random polypropylene, etc. The proportion of the acid-modified polyolefin resin in the resin composition is, for example, 5 to 30% by weight.

[0032] Examples of the method for producing the acid-modified polyolefin resin include a method of graft-modifying an unmodified polyolefin resin with an acid-functional group-containing monomer by melt-kneading, a method of copolymerizing an olefin monomer and an acid-functional group-containing monomer, etc. Examples of the acid-functional group-containing monomer include a carboxylic acid group-containing monomer and an acid anhydride group-containing monomer. Examples of the carboxylic acid group-containing monomer include α,β-unsaturated carboxylic acid monomers such as acrylic acid, methacrylic acid, maleic acid, nadic acid, fumaric acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, tetrahydrophthalic acid, endo-bicyclo[2.2.1]-5-heptene-2,3-dicarboxylic acid (endomethylene tetrahydrophthalic acid). Examples of the acid anhydride group-containing monomer include unsaturated dicarboxylic acid anhydride monomers such as maleic anhydride, nadic anhydride, itaconic anhydride, citraconic anhydride, and endomethylene tetrahydrophthalic anhydride.

[0033] Examples of the method for producing the resin composition include a method of blending a polar main resin, a low-melting-point liquid crystal polymer, and an acid-modified polyolefin resin by a method such as melt-kneading. After blending two of the three types of polar main resin, low-melting-point liquid crystal polymer, and acid-modified polyolefin resin first, the remaining one type may be added and blended. The apparatus for melt-kneading is not particularly limited, and a single-screw extruder, a multi-screw extruder, a Banbury mixer, a plast mill, a heated roll kneader, etc. can be used.

[0034] As a result of blending, in the resin composition, the polar main material resin forms the continuous phase, and the low melting point liquid crystal polymer and the acid-modified polyolefin resin each form the dispersed phase. Since the acid-modified polyolefin resin is well dispersed in the polar main material resin and the low melting point liquid crystal polymer, hydrolysis of ester bonds and the like contained in the polar main material resin and the low melting point liquid crystal polymer can be suppressed even in a high temperature and high humidity environment such as during thermoforming. Furthermore, a decrease in the tensile fracture stress of the resin composition can be suppressed.

[0035] When the total amount of the resin composition is 100 parts by weight, it is preferable that the polar main material resin is in a proportion of 40 to 60 parts by weight, the low melting point liquid crystal polymer is in a proportion of 20 to 40 parts by weight, and the acid-modified polyolefin resin is in a proportion of 5 to 30 parts by weight. It is preferable that the proportion of the polar main material resin is more than the proportion of the low melting point liquid crystal polymer, and it is preferable that the proportion of the low melting point liquid crystal polymer is more than the proportion of the acid-modified polyolefin resin.

[0036] The resin composition may contain optional components. Examples of optional resin components include polyolefin resins, olefin-based elastomers, styrene-based elastomers, and the like. Examples of additives, although not particularly limited, include fillers, colorants, antioxidants, defoaming agents, leveling agents, light absorbers, and the like.

[0037] The resin composition may be a composition that does not contain a high melting point liquid crystal polymer having a crystal melting temperature exceeding 250°C. Furthermore, the resin composition may be a composition that does not contain a resin component having a melting temperature (melting point) exceeding 250°C. The thickness when the resin composition is used as a resin layer is not particularly limited, but examples include 60 to 120 μm.

[0038] The resin composition can be used as an adhesive material, a sealing material, etc. in various electrical devices, electronic equipment, etc. The applications are not particularly limited, but examples include solar cells, fuel cells, electrolysis devices, electrochemical devices, and the like.

[0039] The resin composition may be used for a single-layer resin layer or at least one layer in a multi-layer laminate. When the resin composition is used for a laminate, it may be used for adhesion between layers included in the laminate or for an adhesive layer for another adherend. When the resin composition is used for an adhesive layer, the adhesive layer may be laminated on at least one side of a base material layer such as a base film. An intermediate layer for improving adhesion may be provided between the base material layer and the adhesive layer. Examples of the base film include resin films such as thermoplastic resins.

Examples

[0040] Hereinafter, the present invention will be specifically described with reference to examples.

[0041] A polymer alloy of a polar main material resin and a low melting point liquid crystal polymer and an acid-modified polyolefin resin were melt-kneaded, and the obtained resin composition was formed into a film with a thickness of 90 μm.

[0042] As the polar main material resin and the low melting point liquid crystal polymer, a polymer alloy (trade name: TECROS (registered trademark) T-440HS, manufactured by Ueno Pharmaceutical Co., Ltd., referred to as "PET / LCP" in the table) in which polyethylene terephthalate (PET) and liquid crystal polymer (LCP) were blended at a weight ratio of 60:40 was used. The liquid crystal polymer contained in this polymer alloy is a low melting point liquid crystal polymer having a crystal melting temperature of 220°C.

[0043] As the acid-modified polyolefin resin, a commercially available acid-modified polyethylene (trade name: Admer (registered trademark) SF728, manufactured by Mitsui Chemicals, Inc., referred to as "APE" in the table) was used. In No. 1, only PET / LCP (without APE) was used, in No. 2, the weight ratio of PET / LCP and APE was 90:10, and in No. 3, the weight ratio of PET / LCP and APE was 80:20.

[0044] The measurement of the tensile fracture stress was carried out on samples obtained by punching out the films of the obtained resin layer into dumbbell shapes of No. 5. The measurement was performed under the conditions of a chuck distance of 80 mm, a gauge length of 45 mm, and a tensile speed of 300 mm / min. After preparing each sample so that the tensile direction was the MD direction (flow direction) or the TD direction (width direction), the tensile fracture stress was determined from the cross-sectional area (width 6 mm, thickness 0.09 mm) at the narrow part of the sample width.

[0045] The pressure cooker test (PCT) was carried out under the conditions of 110 °C, 85% RH, and 96 h. The tensile fracture stress before and after PCT was measured for the same sample, and the retention rate before and after PCT was calculated. This retention rate is obtained by (tensile fracture stress after PCT) / (tensile fracture stress before PCT) × 100 (%). The measurement results of the tensile fracture stress are shown in Table 1.

[0046]

Table 1

[0047] The cross-sections cut along the MD direction (MD cross-section) or the TD direction (TD cross-section) of each sample were observed with a scanning electron microscope (SEM), and images were taken. The results are shown in Figures 1 to 6. In all cases, a sea-island structure was formed in which the polar main resin (PET) constituted the sea portion and the liquid crystal polymer (LCP) and the acid-modified polyolefin resin (APO) constituted the island portion. Here, the acid-modified polyolefin resin (APO) is acid-modified polyethylene (APE).

[0048] Next, the measurement method of the tensile fracture stress was changed, and the results of measuring the samples obtained by punching the resulting film into short lengths (10 mm) under the conditions of a chuck distance of 50 mm and a tensile speed of 20 mm / min are shown in Table 2. For No. 4, a commercially available acid-modified polypropylene (trade name: Admer (registered trademark) QB510, manufactured by Mitsui Chemicals, Inc., denoted as "APP" in Table 2) was used as the acid-modified polyolefin resin. For No. 5, a homoPET film (thickness 90 μm) was used. For No. 6, a drawn PET film (thickness 75 μm) was used for reference.

[0049]

Table 2

[0050] As shown in Tables 1 and 2, it was confirmed that by blending the acid-modified polyolefin resin, a decrease in the tensile fracture stress after PCT can be suppressed.

Claims

1. A resin composition containing a polar main material resin other than a liquid crystal polymer, a low melting point liquid crystal polymer having a crystal melting temperature of 250°C or lower, and an acid-modified polyolefin resin, wherein the polar main material resin constitutes a continuous phase, and the low melting point liquid crystal polymer and the acid-modified polyolefin resin each constitute a dispersed phase, forming a sea-island structure.

2. The resin composition according to Claim 1, wherein the polar main material resin is at least one selected from the group consisting of a resin having a hydrocarbon chain as a main chain and having a chlorine atom, an oxygen atom or a nitrogen atom outside the main chain, a resin having an oxygen atom in the main chain, and a resin having a nitrogen atom in the main chain.

3. The resin composition according to Claim 1, wherein the polar main material resin is at least one selected from resins having an oxygen atom in the main chain.

4. The resin composition according to Claim 1, wherein the polar main material resin is a polyester resin other than a liquid crystal polymer.

5. The resin composition according to Claim 1, wherein, based on 100 parts by weight of the entire resin composition, the polar main material resin is 40 to 60 parts by weight, the low melting point liquid crystal polymer is 20 to 40 parts by weight, and the acid-modified polyolefin resin is 5 to 30 parts by weight.

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