JP6874446B2 - Thermoplastic elastomer for carbon fiber reinforced plastic adhesive lamination - Google Patents

Description

The present invention relates to a thermoplastic elastomer used for adhesively laminating between carbon fiber reinforced plastics or as a skin in a carbon fiber reinforced plastic laminate, and a laminated molded product using this thermoplastic elastomer.

Composite materials that use carbon fiber as reinforcing fibers are called carbon fiber reinforced plastics (CFRP), and are used in industries such as aviation materials, golf shafts, tennis rackets and other sports / leisure products, and ship materials. It is used as a material, and in recent years, it has begun to be put into practical use as an automobile part by taking advantage of its light weight and strength characteristics.

Carbon fiber reinforced plastic is excellent in light weight and is attracting attention as a substitute for metal, but it has the disadvantage that it cannot absorb the energy and breaks into pieces at the time of impact or vibration where strong energy is applied. As it is, it is difficult to apply it to structural members and the like.

As an improvement thereof, Patent Document 1 proposes laminating a thermoplastic elastomer layer on carbon fiber reinforced plastic, but the carbon fiber reinforced plastic / thermoplastic elastomer laminate has the following problems.
That is, for example, carbon fiber reinforced plastics in prepregs are generally impregnated with unreacted epoxy resin, and the epoxy resin is solidified by heating and pressurizing in the reaction temperature range of the epoxy resin during molding to form a structure. Is molded as. On the other hand, when the thermoplastic elastomer melts during molding, the molten polymers contribute to adhesion and exert an adhesive effect. Therefore, it is desired that the thermoplastic elastomer is basically composed of components having compatibility and reactivity with the epoxy resin, and is melt-bonded in the molding temperature range of the epoxy resin as much as possible. However, the melting temperature of a general thermoplastic elastomer is higher than the molding temperature range of the epoxy resin, and it is not melted at the molding temperature of the epoxy resin, so that it is not suitable for melt bonding. In addition, since ordinary thermoplastic elastomers do not react with epoxy resins, most thermoplastic elastomers do not adhere to the epoxy resin and are easily peeled off.

On the other hand, there is also a method of molding a molded body of carbon fiber reinforced plastic and then applying an adhesive to attach a thermoplastic elastomer sheet to the surface of the carbon fiber reinforced plastic, but if the structure has a complicated shape, the adhesive There is a problem that it is difficult to apply the adhesive uniformly, the number of steps for applying the adhesive increases, and the time required for manufacturing becomes long.

In order to stably maintain the impact resistance of the structure made of carbon fiber reinforced plastic, the thermoplastic elastomer sheet can be adhered uniformly even with a complicated carbon fiber reinforced plastic structure. It is necessary to have high adhesion that is stable even after aging and does not peel off. Furthermore, from the viewpoint of improving the degree of freedom of manufacturing, even after storing the thermoplastic elastomer sheet, the method of molding using ordinary prepreg should be changed. It is desired to develop a thermoplastic elastomer capable of molding a laminate with carbon fiber reinforced plastic with good adhesion without extending the molding time.

Special Table 2012-523334

The present invention has been made in view of the above-mentioned conventional conditions, can be easily laminated and molded with carbon fiber reinforced plastic, has high adhesion to carbon fiber reinforced plastic, and is integrally molded with carbon fiber reinforced plastic. For carbon fiber reinforced plastic adhesive lamination, which can sufficiently improve the impact resistance of carbon fiber reinforced plastic, and also has good adhesion even after long-term storage and can be laminated with carbon fiber reinforced plastic. It is an object of the present invention to provide a thermoplastic elastomer and a laminated molded product using the thermoplastic elastomer.

As a result of diligent studies to solve the above problems, the present inventor has made a thermoplastic containing a polyester-based thermoplastic elastomer, a specific hydrogenated block copolymer, and a hydrocarbon-based rubber softener in a predetermined ratio. Even if the elastomer has a complicated structure, it can be easily integrally molded with the carbon fiber reinforced plastic in a uniform and adhesive manner, and the impact resistance of the carbon fiber reinforced plastic can be improved by laminating. Moreover, they have found that the thermoplastic elastomer does not impair the moldability and adhesion even after storage, and have reached the present invention.
That is, the gist of the present invention is as follows.

[1] A thermoplastic elastomer used as the thermoplastic elastomer of a laminated molded product of a carbon fiber reinforced plastic and a thermoplastic elastomer, which is made of a polyester-based thermoplastic elastomer for adhesive lamination of carbon fiber reinforced plastics. Thermoplastic elastomer.

[2] A thermoplastic elastomer used as the thermoplastic elastomer of a laminated molded product of carbon fiber reinforced plastic and a thermoplastic elastomer, with respect to 100 parts by mass of the polyester-based thermoplastic elastomer and the polyester-based thermoplastic elastomer. , The following component (a) and component (b) are contained in a total amount of 300 parts by mass or less, and the ratio of the component (a) to the total 100% by mass of the component (a) and the component (b) is 30 to 90. A thermoplastic elastomer for adhesive lamination of carbon fiber reinforced plastic, characterized in that the proportion of the component (b) is 70 to 10% by mass.
Component (a): (A)-(B) block copolymer composed of a vinyl aromatic compound polymer block (A) and a conjugated diene polymer block (B) and / or (A)-(B)-( A) A hydrogenated block copolymer, a hydrogenated block in which at least 90% of the double bonds of the conjugated diene moiety are saturated by hydrogenation and the weight average molecular weight is 80,000 to 1,000,000. Block Polymer component (b): Hydrocarbon-based rubber softener

[3] The polyester-based thermoplastic elastomer is a polyether ester block copolymer mainly composed of a hard segment mainly composed of aromatic polyester and a soft segment mainly composed of an aliphatic polyether, and is mainly a fat. The thermoplastic elastomer for bonding and laminating carbon fiber reinforced plastics according to [1] or [2], which contains 10 to 80% by mass of a soft segment made of a group of polyether.

[4] The carbon fiber reinforced plastic adhesive lamination according to [2], wherein the content of the vinyl aromatic compound polymer block (A) of the hydrogenated block copolymer of the component (a) is 10 to 50% by mass. Thermoplastic elastomer.

[5] The heat for bonding and laminating carbon fiber reinforced plastics according to [2] or [4], wherein the hydrocarbon softener for component (b) is a paraffin oil having a weight average molecular weight of 300 to 2,000. Plastic elastomer.

[6] The laminated molded product having a carbon fiber reinforced plastic and a thermoplastic elastomer layer laminated on the carbon fiber reinforced plastic, wherein the thermoplastic elastomer layer is described in any one of [1] to [5]. A laminated molded product made of a thermoplastic elastomer for carbon fiber reinforced plastic adhesive lamination.

[7] The laminated molded product according to [6], wherein the slidable material layer is laminated on the surface of the thermoplastic elastomer layer opposite to the carbon fiber reinforced plastic.

[8] An automobile part structure composed of the laminated molded product of [6] or [7].

[9] A ship part structure composed of the laminated molded product of [6] or [7].

[10] A power component structure composed of the laminated molded body of [6] or [7].

The thermoplastic elastomer for carbon fiber reinforced plastic adhesive lamination of the present invention can be integrally molded with carbon fiber reinforced plastic by laminating and integrally molding with good followability, uniform and adhesiveness even if it has a complicated structure. The impact resistance of fiber reinforced plastic can be improved.
Moreover, the thermoplastic elastomer of the present invention can sufficiently maintain these effects even after long-term storage without impairing the above-mentioned effects of improving moldability, adhesion, and impact resistance.

The present invention will be described in detail below, but the following description is an example of an embodiment of the present invention, and the present invention is not limited to the following description as long as the gist of the present invention is not exceeded. It can be arbitrarily modified and carried out without departing from the gist of the invention.
In addition, in this invention, when a numerical value or a physical property value is put before and after using "~", it is used as including the value before and after that.

[Thermoplastic elastomer for carbon fiber reinforced plastic adhesive lamination]
The thermoplastic elastomer for adhesive lamination of carbon fiber reinforced plastic of the present invention (hereinafter, referred to as "thermoplastic elastomer of the present invention") is used as the thermoplastic elastomer of a laminated molded product of carbon fiber reinforced plastic and thermoplastic elastomer. The following components (a) and (b) are contained in a total amount of 0 to 300 parts by mass with respect to 100 parts by mass of the polyester-based thermoplastic elastomer and the polyester-based thermoplastic elastomer. , The ratio of the component (a) to the total 100% by mass of the component (a) and the component (b) is 30 to 90% by mass, and the ratio of the component (b) is 70 to 10% by mass. ..
Component (a): (A)-(B) block copolymer composed of a vinyl aromatic compound polymer block (A) and a conjugated diene polymer block (B) and / or (A)-(B)-( A) A hydrogenated block copolymer, a hydrogenated block in which at least 90% of the double bonds of the conjugated diene moiety are saturated by hydrogenation and the weight average molecular weight is 80,000 to 1,000,000. Block Polymer component (b): Hydrocarbon-based rubber softener

<Polyester-based thermoplastic elastomer>
Various polyester-based thermoplastic elastomers are known, but typical ones are mainly hard segments mainly composed of aromatic polyesters and soft segments mainly composed of aliphatic polyethers or aliphatic polyesters. It is a polyether (or polyester) ester block copolymer as a constituent component. Although any of these can be used in the present invention, it is preferable to use a polyether ester block copolymer.

The polyether ester block copolymer is an esterification reaction or an ester exchange reaction using an aliphatic or alicyclic diol having 2 to 12 carbon atoms, an aromatic dicarboxylic acid or an alkyl ester thereof, and an aliphatic polyether as raw materials. It can be obtained by forming an oligomer and then polycondensing it. As the aliphatic and alicyclic diols having 2 to 12 carbon atoms, those usually used as a raw material for polyester, particularly a raw material for thermoplastic polyester-based elastomers can be used. For example, ethylene glycol, 1,2-propylene glycol, trimethylene glycol, 1,4-butanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and the like can be mentioned, among which 1,4-butanediol, Ethylene glycol is preferred, especially 1,4-butanediol. These diols are usually used alone, but mixtures of two or more may be used if desired.

As the aromatic dicarboxylic acid, those generally used as a raw material for polyester, particularly a raw material for polyester-based elastomer, can be used, and examples thereof include terephthalic acid, isophthalic acid, phthalic acid, and 2,6-naphthalenedicarboxylic acid. Be done. Of these, terephthalic acid and 2,6-naphthalenedicarboxylic acid are preferable, and terephthalic acid is particularly preferable. In addition, two or more of these aromatic dicarboxylic acids may be used in combination if desired.
When an alkyl ester of an aromatic dicarboxylic acid is used, the above-mentioned dimethyl ester or diethyl ester of an aromatic dicarboxylic acid is used. Preferred are dimethylterephthalate and 2,6-dimethylnaphthalenedicarboxylate.

Further, in addition to the above diol and dicarboxylic acid components, a trifunctional alcohol, a carboxylic acid, or an ester thereof may be copolymerized in a small amount, and an aliphatic dicarboxylic acid such as adipic acid or a dialkyl ester thereof may be copolymerized in a small amount. It can be used as a polymerization component.

As the aliphatic polyether, poly (alkylene ether) glycol can be used. For example, polyethylene glycol, poly 1,2- (or 1,3-) propylene glycol, poly (tetramethylene ether) glycol, poly (hexamethylene ether) glycol and the like can be mentioned, and poly (tetramethylene ether) is particularly preferable. It is glycol.

The number average molecular weight of the poly (alkylene ether) glycol is usually 400 to 6,000, preferably 600 to 4,000, and particularly preferably 1,000 to 3,000. .. If the soft segment is a poly (alkylene ether) glycol having a number average molecular weight of less than 400, sufficient adhesiveness may not be exhibited. On the other hand, when the number average molecular weight exceeds 6,000, phase separation is likely to occur in the polycondensation system when producing the polyester-based thermoplastic elastomer, and the physical properties of the obtained polyester-based thermoplastic elastomer tend to deteriorate. .. The number average molecular weight referred to here is measured by gel permeation chromatography (GPC). For the calibration of GPC, the POLYTETRAHYDROFURAN calibration kit manufactured by POLYMER LABORATORIES in the United Kingdom may be used.

The content of the aliphatic polyether component of the polyester-based thermoplastic elastomer is usually 10 to 80% by mass, but is preferably 30 to 80% by mass, particularly 50 to 80% by mass. If the content of the aliphatic polyether component is less than 10% by mass, the produced polyester-based thermoplastic elastomer is inferior in heat resistance and oil resistance, and conversely, if it exceeds 80% by mass, the desired physical properties are exhibited even if melt-kneaded. Tends to be difficult. The content of the aliphatic polyether component in the polyester-based thermoplastic elastomer is the amount of protons on the aliphatic carbon atom and the amount of protons on other carbon atoms on the nuclear magnetic resonance spectrum (NMR) chart of protons. It can be calculated from.

The polyester-based thermoplastic elastomer used in the present invention usually has a melting point of 125 ° C. or higher, preferably 140 ° C. or higher, and more preferably 160 ° C. or higher. If the melting point of the polyester-based thermoplastic elastomer is less than the lower limit, the heat resistance of the obtained thermoplastic elastomer is inferior, which is not preferable. The upper limit of the melting point of the polyester-based thermoplastic elastomer is not limited, but is usually 300 ° C. or lower, preferably 260 ° C. or lower. Here, the melting point of the polyester-based thermoplastic elastomer is measured by using a differential scanning calorimeter, raising the temperature from room temperature to 250 ° C. at a heating rate of 100 ° C./min, holding for 3 minutes, and then cooling to −100 ° C. This is the temperature of the melting peak when the temperature is raised again to 250 ° C. at a rate of 10 ° C./min after cooling at a rate of 10 ° C./min.

The MFR (JIS 7210 compliant, 230 ° C., load 2.16 kg) of the polyester-based thermoplastic elastomer used in the present invention is usually 1 to 100 (g / 10 minutes), preferably 3 to 80 (g / 10 minutes), and further. Preferably, it is in the range of 5 to 60 (g / 10 minutes). If the MFR exceeds the above upper limit value, the melt tension may be too small and there may be a problem such as drawdown during molding. If the MFR is less than the above lower limit, the fluidity may be insufficient and the moldability may be deteriorated.

Further, the polyester-based thermoplastic elastomer used in the present invention has a JIS-D hardness (hardness according to durometer and type D according to JIS 6253) of 10 or more and 80 or less, preferably 15 or more and 70 or less, and particularly preferably 20 or more and 60 or less. Those in the range are suitable. If the JIS-D hardness is less than the above lower limit value, the heat resistance tends to be inferior, and if it exceeds the above upper limit value, the rubber elasticity and adhesiveness tend to be inferior.

Only one type of these polyester-based thermoplastic elastomers may be used, or two or more types having different block configurations, physical properties, etc. may be mixed and used.

Commercially available products of such polyester-based thermoplastic elastomers include "Primaloy" (manufactured by Mitsubishi Chemical Corporation, Primaloy is a registered trademark of the company), "Perprene" (manufactured by Toyo Spinning Co., Ltd.), and "Hytrel" (Toray DuPont). (Made by Co., Ltd.), etc.

<Component (a): Hydrogenated block copolymer>
The component (a), which is a constituent component of the thermoplastic elastomer of the present invention, is a (A)-(B) block copolymer composed of a vinyl aromatic compound polymer block (A) and a conjugated diene polymer block (B). And / or a hydrogenated product of the (A)-(B)-(A) block polymer in which at least 90% of the double bonds of the conjugated diene moiety are saturated by hydrogenation and the weight average molecular weight is It is a hydrogenated block copolymer of 80,000 to 1,000,000 (hereinafter, may be referred to as “hydrogenated block copolymer (a)”).

Vinyl aromatic compound Examples of the vinyl aromatic compound constituting the polymer block (A) include styrene, t-butylstyrene, α-methylstyrene, o-, m-, p-methylstyrene, and 1,3-dimethylstyrene. , Vinyl naphthalene, vinyl anthracene and the like, and one or more kinds thereof, and styrene and α-methylstyrene are particularly preferable.

Examples of the conjugated diene monomer constituting the conjugated diene polymer block (B) include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 2-methyl-1,3-. One or more of pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadien, 3-butyl-1,3-octadien and the like can be mentioned, in particular butadiene, isoprene, or butadiene / isoprene. A mixture having a mass ratio of 2/8 to 6/4 of the above is preferable.

When the conjugated diene monomer is composed only of butadiene, a block copolymer obtained by hydrogenating 20 to 80% of the 1,2-addition structure in the microstructure of the polybutadiene block is preferable, particularly 1, 2-Preferably, the addition structure is 30 to 60%.

The molecular structure of the block copolymer of component (a) may be linear, branched, radial, or a combination thereof.

The component (a) is a hydrogenated block copolymer obtained by hydrogenating the block copolymer, and the hydrogenation rate thereof is two of the conjugated diene portion of the conjugated diene polymer block which is the block (B). The hydrogenation rate of the double bond is 90% or more, preferably 95 to 100%.

The content of the vinyl aromatic compound polymer block (A) in the hydrogenated block copolymer (a) is preferably 10 to 50% by mass, more preferably 15 to 45% by mass, and further preferably 20 to 40%. It is mass%. If the content of the vinyl aromatic compound polymer block (A) is less than 10% by mass, mechanical properties such as tensile strength and heat resistance tend to be inferior, and if it exceeds 50% by mass, flexibility and rubber elasticity are inferior. Bleed of the hydrocarbon-based rubber softening agent of the component (b) described later tends to occur.

The weight average molecular weight of the hydrogenated block copolymer (a) is 80,000 to 1,000,000 in terms of polystyrene as measured by gel permission chromatography, but is preferably 100,000 to 600,000, more preferably 100,000 to 600,000. It is 150,000 to 400,000. When the weight average molecular weight is less than 80,000, the rubber elasticity and mechanical strength are lowered, and the bleeding of the hydrocarbon-based rubber softening agent of the component (b) described later is likely to occur. On the other hand, when the weight average molecular weight exceeds 1 million, the fluidity is poor and molding becomes difficult.

The method for producing such a hydrogenated block copolymer (a) may be any method as long as the above structure and physical properties can be obtained. For example, the method described in Tokusho No. 40-23798 and the method of performing block polymerization in an inert solvent in the presence of a lithium catalyst can be adopted. Further, the hydrogenation treatment of these block copolymers is described in, for example, JP-A-42-8704, JP-A-43-6636, JP-A-59-133203, JP-A-60-79005 and the like. The methods described can be carried out in the presence of a hydrogenation catalyst in an inert solvent.

The hydrogenated block copolymer of the component (a) may be a block copolymer in which the polymer molecular chain is extended or branched via a coupling agent residue. Examples of the coupling agent used in this case include diethyl adipate, divinylbenzene, tetrachlorosilicon, butyltrichlorosilicon, tetrachlorotin, butyltrichlorotin, 1,2-dibromoethane, 1,4-chloromethylbenzene, and the like. Examples thereof include bis (tricrosssilyl) ethane, epoxidized flaxseed oil, tolylene diisocyanate, 1,2,4-benzenetriisocyanate and the like.

Commercially available products of such hydrogenated block copolymer (a) include products such as "KRATON-G" (Kraton Polymer Co., Ltd.), "Septon" (Kuraray Co., Ltd.), and "Tough Tech" (Asahi Kasei Chemicals Co., Ltd.). It can be exemplified.

As the hydrogenated block copolymer (a), only one type may be used, or two or more types having different block configurations, physical properties, etc. may be mixed and used.

<Component (b): Hydrocarbon-based rubber softener>
The component (b), which is a constituent component of the thermoplastic elastomer of the present invention, is a hydrocarbon-based rubber softener (hereinafter, may be referred to as "hydrocarbon-based rubber softener (b)").

As the hydrocarbon-based rubber softener (b), a hydrocarbon having a weight average molecular weight of usually 300 to 2,000, preferably 500 to 1,500 is used, and a mineral oil-based hydrocarbon or a synthetic resin-based hydrocarbon is used. Suitable. Here, the weight average molecular weight is a polystyrene-equivalent molecular weight measured by gel permission chromatography.

Generally, the softening agent for mineral oil-based rubber is a mixture of aromatic hydrocarbons, naphthenic hydrocarbons, and paraffinic hydrocarbons. Aromatic oils with a carbon content of 35% by mass or more of aromatic hydrocarbons, and naphthenic oils and paraffinic hydrocarbons with a naphthenic hydrocarbon ratio of 30 to 45% by mass with respect to the total carbon content. Those having a carbon content of 50% by mass or more are called paraffinic oils. In the present invention, paraffinic oil is preferably used.

Only one type of softening agent (b) for hydrocarbon rubber may be used, or two or more types may be mixed and used.

<Mixing ratio>
The thermoplastic elastomer of the present invention may be composed of only a polyester-based thermoplastic elastomer, and may contain the polyester-based thermoplastic elastomer and the above-mentioned components (a) and (b).
When the thermoplastic elastomer of the present invention contains the component (a) and the component (b), the content thereof is the total amount of the component (a) and the component (b) with respect to 100 parts by mass of the polyester-based thermoplastic elastomer. It is 300 parts by mass or less, preferably 1 to 200 parts by mass. If the total amount of the component (a) and the component (b) exceeds this range, the adhesion to the carbon fiber reinforced plastic deteriorates.

The composition ratio of the component (a) and the component (b) is such that the component (a) is 30 to 90% by mass and the component (b) is 70 to 10% by mass in the total of 100% by mass, preferably. The component (a) is 35 to 80% by mass, and the component (b) is 65 to 20% by mass. If the amount of the component (a) is less than this range and the amount of the component (b) is large, the heat resistance of the obtained thermoplastic elastomer is inferior or bleeding occurs. On the other hand, if the component (a) is larger than this range and the component (b) is smaller, the flexibility and moldability deteriorate.

<Organic peroxide>
The thermoplastic elastomer of the present invention is obtained by heating and mixing the above-mentioned polyester-based thermoplastic elastomer or the above-mentioned polyester-based thermoplastic elastomer with components (a) and (b) using a mixer such as an extruder. , But at that time, an organic peroxide or a cross-linking aid may be mixed and cross-linked.

Specific examples of the organic peroxide include dimethyl peroxide, g-t-butyl peroxide, 2,5-dimethyl-2,5-di- (t-butylperoxy) hexane, and 2,5-dimethyl-2,5-. Di- (t-butylperoxy) hexin-3,1,3-bis (t-butylperoxyisopropyl) benzene, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl -4,4,5-bis (t-butylperoxy) peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, t-butylperoxybenzoate, t-butylperoxyisopropyl carbonate, diacetylperoxide, lauroyl peroxide , T-butylcumyl peroxide and the like, preferably 2,5-dimethyl-2,5-di- (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di- (t). -Butylperoxy) Hexin-3,1,3-bis (t-butylperoxyisopropyl) benzene, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4 , -Bis (t-butylperoxy) valerate. These organic peroxides can be used alone or in admixture of two or more.

The organic peroxide is usually used in the range of 0.05 to 3 parts by mass, preferably 0.1 to 2 parts by mass with respect to a total of 100 parts by mass of the component (a) and the component (b).

In the cross-linking treatment with these organic peroxides, sulfur, p-quinone dioxime, p, p'-dibenzoylquinone dioxime, N-methyl-N-4-dinitrosoaniline, nitrosobenzene, diphenylguanidine, trimesterolpropane Peroxy cross-linking aids such as -N, N'-m-phenylenedi maleimide, divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylpropantrimethacrylate, allyl methacrylate Polyfunctional methacrylate monomers such as, etc., and polyfunctional vinyl monomers such as vinyl butyrate and vinyl acetate can be blended.

The cross-linking aid, polyfunctional methacrylate or polyfunctional vinyl polymer is usually 0.1 to 5 parts by mass, preferably 0.2 to 5 parts by mass, based on 100 parts by mass of the total amount of the component (a) and the component (b). Used in 4 parts by mass.

<Other ingredients>
The thermoplastic elastomer of the present invention includes various additives such as stabilizers, lubricants, antioxidants, ultraviolet absorbers, foaming agents, flame retardants, colorants, fillers, and others other than essential components, if necessary. The thermoplastic resin or rubber of the above may be blended.

Of these, it is particularly preferable to add an antioxidant as a stabilizer. Examples of the antioxidant include monophenols, bisphenols, polyphenols of birds and above, thiobisphenols, naphthylamines, diphenylamines, and phenylenediamines. Among these, monophenol-based, bisphenol-based, polyphenol-based triphenols and thiobisphenol-based antioxidants are preferable. When an antioxidant is blended, the amount of the antioxidant added is usually 0.01 to 5 parts by mass, preferably 0.% by mass, based on 100 parts by mass of the total of the polyester-based thermoplastic elastomer, the component (a) and the component (b). It is 05 to 3 parts by mass. If the amount added is less than 0.01 parts by mass, the effect of the antioxidant is difficult to obtain, and if it exceeds 5 parts by mass, the improving effect commensurate with the amount added cannot be obtained, which is not preferable in terms of cost.

Examples of the thermoplastic resin other than the essential components include polyphenylene ether-based resin, polyamide-based resin such as nylon 6 and nylon 66, polyester-based resin such as polyethylene terephthalate and polybutylene terephthalate, polyoxymethylene homopolymer, and polyoxymethylene copolymer. Examples thereof include polyoxymethylene-based resins, polymethylmethacrylate-based resins, polystyrene-based resins, biodegradable resins, and plant-derived raw material resins.
Examples of the rubber include olefin rubber such as ethylene / propylene copolymer rubber, ethylene / propylene / non-conjugated diene copolymer rubber, polybutadiene rubber, and styrene copolymer rubber other than essential components. it can.

<Manufacturing method of thermoplastic elastomer>
The thermoplastic elastomer of the present invention is required to be a polyester-based thermoplastic elastomer or a polyester-based thermoplastic elastomer, a component (a): a hydrogenated block copolymer, and a component (b): a softener for a hydrocarbon-based rubber. It is produced by heating and kneading a blend of thermoplastic elastomers containing organic peroxides, cross-linking aids, various additives, etc., which are blended according to the above.

In the production of the thermoplastic elastomer of the present invention, a Henschel mixer, a ribbon blender, a V-type blender or the like is used as a mixing device, and as a kneading device, a mixing roll, a kneader, a Banbury mixer, a brabender plastograph, a uniaxial extrusion or the like is used. A machine or twin-screw extruder is used.

<Molding of thermoplastic elastomer>
The thermoplastic elastomer of the present invention can be molded by a molding machine such as an injection molding machine, a single-screw extrusion molding machine, a twin-screw extrusion molding machine, a compression molding machine, or a calendar processing machine, and the molded product is laminated with prepreg CFRP. Various structures can be obtained by integrally molding and compounding.

[Laminate molded body]
The laminated molded article of the present invention has a carbon fiber reinforced plastic and a thermoplastic elastomer layer made of the thermoplastic elastomer of the present invention laminated on the carbon fiber reinforced plastic, and the carbon fiber reinforced plastic and the carbon fiber reinforced. A thermoplastic elastomer layer may be laminated as an intermediate layer between the plastic and the carbon fiber reinforced plastic, or a thermoplastic elastomer layer may be laminated as a skin on the carbon fiber reinforced plastic.
Further, a layer of a slidable material may be further laminated on a thermoplastic elastomer layer laminated on a carbon fiber reinforced plastic.

As the carbon fiber reinforced plastic, a carbon fiber reinforced epoxy resin is usually used, but the resin type of the carbon fiber reinforced plastic is not limited to the epoxy resin.

Further, as the slidable material used for the surface layer, silane cross-linked polyethylene or the like can be used.

The impact resistance of such a laminated molded product of the present invention is greatly improved by a thermoplastic elastomer laminated with carbon fiber reinforced plastic with good adhesion, and various automobile parts structures and other marine parts structures are used. , Power component structures, building component structures, etc., but among them, it is suitable for automobile applications where weight reduction is strongly desired, and in these applications, the effect of improving the impact resistance of the present invention. Is fully demonstrated.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples as long as the gist thereof is not exceeded. The values of various production conditions and evaluation results in the following examples have meanings as preferable values of the upper limit or the lower limit in the embodiment of the present invention, and the preferable range is the above-mentioned upper limit or lower limit value. , The range specified by the combination of the values of the following examples or the values of the examples may be used.

[raw materials]
The following raw materials were used in the following examples.

<Polyester elastomer>
TPEE-1: Polybutylene terephthalate-polytetramethylene ether block copolymer Number of polytetramethylene ether units Average molecular weight: 2000
Content of polytetramethylene ether unit: 77% by mass
Content of polybutylene terephthalate unit: 23% by mass
Melting point (measured by DSC device): 150 ° C
MFR (measurement temperature 230 ° C., measurement load 21.18N): 25g / 10 minutes Duro A hardness: 75
TPEE-2: Polybutylene terephthalate-polytetramethylene ether block copolymer Number of polytetramethylene ether units Average molecular weight: 2000
Content of polytetramethylene ether unit: 70% by mass
Content of polybutylene terephthalate unit: 30% by mass
Melting point (measured by DSC device): 160 ° C
MFR (measurement temperature 230 ° C., measurement load 21.18N): 25g / 10 minutes Duro D hardness: 26

<Component (a): Hydrogenated block copolymer>
SB-1: Hydrogenated product of copolymer of styrene block-butadiene block-styrene block Styrene content: 32% by mass
Hydrogenation rate: 98% or more Weight average molecular weight: Approximately 220,000

<Component (b): Hydrocarbon-based rubber softener>
OIL-1: Paraffin oil ("Diana Process Oil PW-90" manufactured by Idemitsu Kosan Co., Ltd.)
Weight average molecular weight: 550
Viscosity at 40 ° C: 96 mm ² / sec

[Evaluation method]
The obtained thermoplastic elastomer was evaluated by the following method.

<Maximum peel strength>
The thermoplastic elastomer sheet obtained in each example was sandwiched between two sheets of CFRP prepreg (20 cm square, thickness 0.35 mm) impregnated with epoxy resin, and placed in an autoclave at 130 ° C. and a pressure of 0.5 MPa. The mixture was heat-bonded for 4 hours to obtain a laminated molded body in which a thermoplastic elastomer sheet was laminated between CFRP sheets.
A notch with a width of 25 mm is made in one CFRP sheet and the thermoplastic elastomer sheet of the obtained laminated molded product, and the other CFRP sheet and the thermoplastic elastomer are peeled off, and the edge of the CFRP sheet and the CFRP sheet and heat are peeled off. The maximum peel strength was measured by attaching the ends on which the thermoplastic elastomer sheets were laminated to the chucks of the autograph and peeling them by 180 °.

<Impact test>
Using the DuPont impact test on the sheet surface of the laminated molded product prepared in the same manner as in the above evaluation of adhesion strength, a 1 kg weight was placed at room temperature from a height of 30 cm with a shooting type of φ0.625 inch. After dropping, the cracking condition of the laminated molded product was observed and evaluated according to the following criteria.
Further, as Comparative Example 3, a laminated molded product was obtained in the same manner as in the above-mentioned maximum peel strength by using only the CFRP prepreg without using the thermoplastic elastomer sheet, and the same was applied to the CFRP-only laminated molded product. An impact test was performed and evaluated.
◯: The CFRP sheet remains unbroken.
X: The CFRP sheet is broken.

<Maximum peel strength after long-term storage>
After the thermoplastic elastomer sheet obtained in each example was left at room temperature for 3 months, a laminated molded product was prepared in the same manner as in the evaluation of the maximum peel strength described above, and the obtained laminated molded product was subjected to the above-mentioned maximum peeling. The maximum peel strength of 180 ° was measured in the same manner as the strength.

[Examples 1 to 3 and Comparative Examples 1 to 2]
<Preparation of thermoplastic elastomer>
Tetrakiss [methylene-3- (3', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane (Ciba Specialty Chemicals Co., Ltd.) as a stabilizer with respect to the blending amount shown in Table-1. "Irganox 1010") 0.1 parts by mass is added, mixed with a Henschel mixer, and extruded with a JSW twin-screw extruder "TEX30" at 210 ° C. and a screw rotation speed of 400 rpm using a heavy-duty feeder. To obtain a thermoplastic elastomer composition.

<Manufacturing of thermoplastic elastomer sheet>
This thermoplastic elastomer was press-molded with a press at a temperature of 200 ° C. to prepare a sheet having a thickness of 1 mm.

Each evaluation was performed using the obtained thermoplastic elastomer sheet, and the results are shown in Table 1-1.

From Table 1, the thermoplastic elastomer of the present invention can be easily laminated with carbon fiber reinforced plastic to obtain a laminated molded product with high adhesion, and the impact resistance of carbon fiber reinforced plastic can be significantly improved. It turns out that it can be improved. Further, it can be seen that the thermoplastic elastomer of the present invention can secure adhesion even in molding after long-term storage, and can provide a carbon fiber reinforced plastic laminated molded product having high adhesion and can be used for durable applications.

On the other hand, the laminated molded product of Comparative Example 3 in which the thermoplastic elastomer is not laminated has poor impact resistance. In Comparative Example 1 in which the thermoplastic elastomer does not contain the polyester-based thermoplastic elastomer, the adhesion to CFRP is poor. Further, even if the polyester-based thermoplastic elastomer was contained, the adhesiveness was inferior even in Comparative Example 2 in which the content ratio was small.

Claims (9)

It is a thermoplastic elastomer used as the thermoplastic elastomer of a laminated molded product of a carbon fiber reinforced plastic impregnated with an epoxy resin and a thermoplastic elastomer, and the polyester-based thermoplastic elastomer and 100 parts by mass of the polyester-based thermoplastic elastomer are used. On the other hand, the following component (a) and component (b) are contained in a total amount of 300 parts by mass or less, and the ratio of the component (a) to the total 100% by mass of the component (a) and the component (b) is 30. A thermoplastic elastomer for adhesive lamination of carbon fiber reinforced plastic, characterized in that the proportion of the component (b) is 70 to 10% by mass in an amount of about 90% by mass.
Component (a): (A)-(B) block copolymer composed of a vinyl aromatic compound polymer block (A) and a conjugated diene polymer block (B) and / or (A)-(B)-( A) A hydrogenated block copolymer, a hydrogenated block in which at least 90% of the double bonds of the conjugated diene moiety are saturated by hydrogenation and the weight average molecular weight is 80,000 to 1,000,000. Block Polymer component (b): Hydrocarbon-based rubber softener The polyester-based thermoplastic elastomer is a polyether ester block copolymer mainly composed of a hard segment mainly composed of aromatic polyester and a soft segment mainly composed of an aliphatic polyether, and is mainly an aliphatic polyether. The thermoplastic elastomer for adhesive lamination of carbon fiber reinforced plastic according to claim 1, wherein the soft segment composed of 10 to 80% by mass is contained. The heat for bonding and laminating carbon fiber reinforced plastics according to claim 1 or 2, wherein the content of the vinyl aromatic compound polymer block (A) of the hydrogenated block copolymer of the component (a) is 10 to 50% by mass. Plastic elastomer. The heat for adhesive lamination of carbon fiber reinforced plastic according to any one of claims 1 to 3, wherein the hydrocarbon softener of the component (b) is a paraffin oil having a weight average molecular weight of 300 to 2,000. Plastic elastomer. A laminated molded product having a carbon fiber reinforced plastic and a thermoplastic elastomer layer laminated on the carbon fiber reinforced plastic, wherein the thermoplastic elastomer layer is the carbon fiber reinforced according to any one of claims 1 to 4. A laminated molded product made of a thermoplastic elastomer for plastic adhesive lamination. The laminated molded article according to claim 5 , wherein a slidable material layer is laminated on a surface of the thermoplastic elastomer layer opposite to the carbon fiber reinforced plastic. An automobile part structure composed of the laminated molded product according to claim 5 or 6. A ship part structure composed of the laminated molded product according to claim 5 or 6. A power component structure comprising the laminated molded body of claim 5 or 6.