JP6234684B2 - Manufacturing method of adhesive body - Google Patents

Description

  The present invention uses insert films (for example, ceramics, metals and synthetic materials) using a film made of a thermoplastic polymer composition having excellent flexibility, mechanical properties, molding processability, and heat resistance without performing primer treatment. Resin), the film, and a resin member.

  Ceramics, metals, and synthetic resins with excellent durability, heat resistance, and mechanical strength are widely used in various applications such as home appliances, electronic parts, machine parts, and automobile parts. These members may be used by adhering or combining different materials depending on applications, component configurations, and usage methods.

The method of adhering or compounding different types of materials is a method of adhering using an adhesive, a method in which a fixing member such as a folded piece or a nail is provided on the member, and fixing both using the fixing member, a screw, etc. And joining methods. However, a composite product in which dissimilar materials are integrated without using an adhesive has a problem in that shape processing is required and the component structure is limited or the design property is lowered.
In addition, when a solvent-based adhesive is used as an adhesive, there is a concern that the working environment may be deteriorated due to VOC, or a non-stick rate is lowered due to poor adhesion due to coating unevenness, poor appearance of a molded product due to stringing, etc. . Furthermore, with a solvent-based adhesive, a drying process is essential after application, which is not economical because the equipment is enlarged and the tact time of production becomes long.
On the other hand, it is known that insert molding is also suitable as a method for efficiently obtaining a composite product obtained by combining different materials. However, combinations of materials that are firmly bonded by insert molding are limited, and in particular, combinations of nonpolar resins / polar resins, synthetic resins / metals, synthetic resins / ceramics, and the like are difficult to bond. Patent Document 1 discloses a method for producing a difficult-to-adhere bonded body by primer treatment on the surface of an insert member. However, there is a problem in that the working environment is deteriorated by VOC and the tact time is increased by a drying process.
As a method for efficiently obtaining an adhesive body by insert molding while avoiding such primer treatment, Patent Document 2 discloses a film made of a modified polyolefin resin in which an insert member made of metal and a resin member have surface adhesiveness. An insert molded body bonded by use is disclosed. Patent Document 3 discloses an insert-molded body using a film made of a modified polyolefin resin and a laminated film of a thermoplastic resin, as in Patent Document 2.

  On the other hand, Patent Documents 4 to 8 describe thermoplastic polymer compositions containing a styrene-based thermoplastic elastomer, an adhesion-imparting component, a compatibilizing agent, a softening agent, and the like.

JP-A-6-299089 JP2012-062423A International Publication No. 12/060311 Pamphlet International Publication No. 09/081877 Pamphlet International Publication No. 11/12596 Pamphlet International Publication No. 12/005270 Pamphlet International Publication No. 12/026501 Pamphlet International Publication No. 12/014757 Pamphlet

However, the film in the method disclosed in Patent Document 2 has a problem that the surface adhesiveness is high, so that the handleability is poor and the productivity is low. The laminated film disclosed in Patent Document 3 requires film lamination. Moreover, it is necessary to change the composition of the laminated film depending on the type of resin of the resin member to be bonded, and there is a problem that not only the process is complicated but also the productivity is lowered and the manufacturing cost is increased.
As described above, the molded bodies disclosed in Patent Documents 2 and 3 and the manufacturing method thereof have room for further improvement.
Thus, the object of the present invention is to bond a film made of a thermoplastic polymer composition excellent in flexibility, mechanical properties, molding processability, and heat resistance to an insert member without applying a primer treatment or the like. An object of the present invention is to provide a method of manufacturing an adhesive body formed by bonding a resin member thereon by insert molding.

According to the present invention, the above object is
<1 >
Polyvinyl acetal with respect to 100 parts by mass of a block copolymer having a polymer block containing an aromatic vinyl compound unit and a polymer block containing a conjugated diene compound unit or a hydrogenated product of the thermoplastic elastomer (A) A block copolymer having 10 to 100 parts by mass of a resin (B1), a polymer block containing an aromatic vinyl compound unit, and a polymer block containing a conjugated diene compound unit, or a hydrogenated product thereof, which is polar A method for producing an adhesive body, in which a film made of a thermoplastic polymer composition containing a thermoplastic elastomer (C2) having a group is bonded to an insert member, and then a resin member is insert-molded on the film;
<2>
The method for producing an adhesive body according to < 1 >, wherein the polyvinyl acetal resin (B1) is polyvinyl butyral;
<3>
A polar group with respect to 100 parts by mass of a block copolymer having a polymer block containing an aromatic vinyl compound unit and a polymer block containing a conjugated diene compound unit or a hydrogenated product of the thermoplastic elastomer (A) A block copolymer having 10 to 100 parts by mass of the polypropylene-containing resin (B2), a polymer block containing an aromatic vinyl compound unit, and a polymer block containing a conjugated diene compound unit, or a hydrogenated product thereof. Then, a film made of a thermoplastic polymer composition containing a compatibilizer (C) which is a thermoplastic elastomer (C2) having a polar group is bonded to an insert member, and then a resin member is insert-molded on the film A method for producing an adhesive;
< 4 >
The thermoplastic elastomer (A) is a polymer block containing an aromatic vinyl compound unit, an isoprene unit, a butadiene unit or an isoprene in which the amount of 1,2-bond and 3,4-bond is 40 mol% or more in total. / The manufacturing method of the adhesive body in any one of <1>-< 3 > which is a block copolymer which has a polymer block containing a butadiene unit, or its hydrogenated product;
< 5 >
The method for producing an adhesive body according to any one of <1> to < 4 >, wherein the film is a single layer film;
< 6 >
The method for producing an adhesive body according to any one of <1> to < 5 >, wherein the insert member is at least one selected from the group consisting of ceramics, metals, thermoplastic resins, and thermosetting resins;
< 7 >
A method for producing an adhesive body according to any one of <1> to < 6 >, wherein a film comprising the thermoplastic polymer composition is bonded to an insert member by heating, and the heating temperature is 120 to 240 ° C ;
Is achieved by providing
The present invention is an invention according to the above <1> to < 7 >, but other matters (for example, the following [1] to [8]) are also described below.
[1]
Adhesion imparted to 100 parts by mass of a block copolymer having a polymer block containing an aromatic vinyl compound unit and a polymer block containing a conjugated diene compound unit or its hydrogenated thermoplastic elastomer (A) A method for producing an adhesive body, in which a film made of a thermoplastic polymer composition containing 10 to 100 parts by mass of component (B) is bonded to an insert member, and then a resin member is insert-molded on the film;
[2]
The method for producing an adhesive body according to [1], wherein the adhesion-imparting component (B) is a polyvinyl acetal resin (B1) and / or a polar group-containing polypropylene resin (B2);
[3]
The method for producing an adhesive body according to [2], wherein the polyvinyl acetal resin (B1) is polyvinyl butyral;
[4]
The thermoplastic polymer composition further comprises a polar group-containing polyolefin copolymer (excluding the polar group-containing polypropylene resin (B2)) (C1), and a polymer block containing an aromatic vinyl compound unit; A block copolymer having a polymer block containing a conjugated diene compound unit or a hydrogenated product thereof, containing a compatibilizer (C) selected from thermoplastic elastomers (C2) having a polar group, [2] or [3] method for producing an adhesive body;
[5]
The adhesive of [4], wherein the polar group-containing polyolefin copolymer (C1) is an olefin copolymer obtained by polymerizing an olefin copolymerizable monomer and a polar group-containing copolymerizable monomer. Body manufacturing method;
[6]
The thermoplastic elastomer (A) is a polymer block containing an aromatic vinyl compound unit, an isoprene unit, a butadiene unit or an isoprene in which the amount of 1,2-bond and 3,4-bond is 40 mol% or more in total. / A method for producing an adhesive body according to any one of [1] to [5], which is a block copolymer having a polymer block containing a butadiene unit or a hydrogenated product thereof;
[7]
The method for producing an adhesive body according to any one of [1] to [6], wherein the insert member is at least one selected from the group consisting of ceramics, metals, thermoplastic resins, and thermosetting resins;
[8]
A method for producing an adhesive body according to any one of [1] to [7], wherein a film comprising a thermoplastic polymer composition is bonded to an insert member by heating, and the heating temperature is 120 to 240 ° C;
Is achieved by providing

According to the production method of the present invention, an insert member such as ceramics, metal, or synthetic resin, a film made of a thermoplastic polymer composition, and a resin member can be easily and firmly obtained without applying a primer treatment. A bonded adhesive body can be provided. In addition, according to this manufacturing method, of course, the adhesive body which bonded the insert member which gave the primer process etc., the film which consists of a thermoplastic polymer composition, and the resin member can also be provided.
Furthermore, according to the manufacturing method of the present invention, an adhesive body with resin members made of various resins can be molded. For example, a resin member made of a thermoplastic resin and a resin member made of a thermosetting resin It can also be formed on a film. The molded body thus obtained has improved design freedom and is firmly bonded, so that it can be used for applications requiring higher adhesive strength.

It is a schematic diagram of an example of a metal mold | die for demonstrating embodiment of this invention. It is a schematic diagram of an example of a metal mold | die for demonstrating embodiment of this invention. It is a perspective view which shows one Example of the adhesive body shape | molded by the manufacturing method of this invention.

The method for producing an adhesive of the present invention comprises a block copolymer having a polymer block containing an aromatic vinyl compound unit and a polymer block containing a conjugated diene compound unit or a thermoplastic elastomer (hydrogenated product thereof). A) A film made of a thermoplastic polymer composition containing 10 to 100 parts by mass of an adhesion-imparting component (B) with respect to 100 parts by mass (hereinafter sometimes abbreviated as “thermoplastic elastomer (A)”). Bonded to an insert member (a film made of a thermoplastic polymer composition bonded to an insert member may simply be abbreviated as “insert member”), and then an adhesive body in which a resin member is insert-molded on the film It is a manufacturing method.
First, a thermoplastic polymer composition and an adhesive will be described, and then a method for manufacturing the adhesive by insert molding will be described.

[Thermoplastic polymer composition]
A thermoplastic polymer composition contains 10-100 mass parts of adhesion | attachment provision components (B) with respect to 100 mass parts of thermoplastic elastomers (A).
Moreover, the thermoplastic polymer composition may further contain a compatibilizer (C), a tackifier resin (D), a softener (E), and the like. Hereinafter, the components (A) to (E) will be described in order.

(Thermoplastic elastomer (A))
The thermoplastic elastomer (A) contained in the thermoplastic polymer composition imparts flexibility, good mechanical properties, moldability, etc. to the thermoplastic polymer composition. To play a role.

-Polymer block containing aromatic vinyl compound units-
Examples of the aromatic vinyl compound constituting the polymer block containing the aromatic vinyl compound unit include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, Examples include 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, 1-vinylnaphthalene, and 2-vinylnaphthalene. The polymer block containing the aromatic vinyl compound unit may be composed of a structural unit derived from only one of these aromatic vinyl compounds, or may be composed of a structural unit derived from two or more types. . Of these, styrene, α-methylstyrene, and 4-methylstyrene are preferable.

Here, in the present invention, the “polymer block containing an aromatic vinyl compound unit” is preferably a polymer block containing 80% by mass or more of an aromatic vinyl compound unit, more preferably an aromatic vinyl compound unit 90. A polymer block containing at least mass%, more preferably a polymer block containing 95% by mass or more of aromatic vinyl compound units (both are values in terms of raw material charge amount). The polymer block containing the aromatic vinyl compound unit may have only the aromatic vinyl compound unit. However, as long as the effect of the present invention is not impaired, other copolymerizable units are used together with the aromatic vinyl compound unit. It may have a monomer unit.
Examples of other copolymerizable monomers include 1-butene, pentene, hexene, butadiene, isoprene, and methyl vinyl ether. In the case of having other copolymerizable monomer units, the proportion thereof is preferably 20% by mass or less, more preferably 10%, based on the total amount of the aromatic vinyl compound unit and other copolymerizable monomer units. It is at most 5% by mass, more preferably at most 5% by mass.

-Polymer block containing conjugated diene compound unit-
Examples of the conjugated diene compound constituting the polymer block containing the conjugated diene compound unit include butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and the like. Can be mentioned. Of these, butadiene and isoprene are preferable.
The polymer block containing a conjugated diene compound unit may be composed of a structural unit derived from only one of these conjugated diene compounds, or may be composed of a structural unit derived from two or more types. In particular, it is preferably composed of a structural unit derived from butadiene or isoprene or a structural unit derived from butadiene and isoprene.

The bonding form of the conjugated diene constituting the polymer block containing the conjugated diene compound unit is not particularly limited. For example, in the case of butadiene, 1,2-bond and 1,4-bond can be formed, and in the case of isoprene, 1,2-bond, 3,4-bond and 1,4-bond can be formed. Among them, when the polymer block composed of conjugated diene compound units is composed of butadiene, when composed of isoprene, or when composed of both butadiene and isoprene, the amount of 1,2-bond in the polymer block composed of conjugated diene compound units The total amount of 3,4-bonds is preferably 1 to 99 mol%, more preferably 35 to 98 mol%, still more preferably 40 to 90 mol%, and 50 to 80 mol%. It is more preferable that
The thermoplastic elastomer (A) is a polymer block containing an aromatic vinyl compound unit, an isoprene unit, a butadiene unit or an isoprene in which the amount of 1,2-bond and 3,4-bond is 40 mol% or more in total. / A block copolymer having a polymer block containing a butadiene unit or a hydrogenated product thereof is preferable.
The total amount of 1,2-bond and 3,4-bond can be calculated by ¹ H-NMR measurement. Specifically, the integrated value of the peak existing at 4.2 to 5.0 ppm derived from 1,2-bond and 3,4-bond units and 5.0 to 5. derived from 1,4-bond units. It can be calculated from the ratio with the integrated value of the peak existing at 45 ppm.

In the present invention, the “polymer block containing a conjugated diene compound unit” is preferably a polymer block containing 80% by mass or more of a conjugated diene compound unit, more preferably a polymer block containing 90% by mass or more of a conjugated diene compound unit. A polymer block, more preferably a polymer block containing 95% by mass or more of conjugated diene compound units (both are values in terms of raw material charge amount). The polymer block containing the conjugated diene compound unit may have only the conjugated diene compound unit, but unless it interferes with the present invention, the polymer block contains other copolymerizable monomer units together with the conjugated diene compound unit. You may have.
Examples of other copolymerizable monomers include styrene, α-methylstyrene, 4-methylstyrene, and the like. In the case of having other copolymerizable monomer units, the proportion thereof is preferably 20% by mass or less, more preferably 10% by mass with respect to the total amount of the conjugated diene compound unit and the other copolymerizable monomer units. % Or less, more preferably 5% by mass or less.

The bonding form of the polymer block containing the aromatic vinyl compound unit and the polymer block containing the conjugated diene compound in the thermoplastic elastomer (A) is not particularly limited, and is linear, branched, radial, or these Any of the bonding forms in which two or more are combined may be used, but a linear bonding form is preferable.
As an example of the linear bond form, when a polymer block containing an aromatic vinyl compound unit is represented by a and a polymer block containing a conjugated diene compound is represented by b, a di represented by ab. A block copolymer, a triblock copolymer represented by a-ba or b-a-b, a tetrablock copolymer represented by abb-ab, abb-ab -A or b-a-b-a-b pentablock copolymer, (а-b) nX type copolymer (X represents a coupling residue, and n represents an integer of 2 or more. ), And mixtures thereof. Among these, a triblock copolymer is preferable, and a triblock copolymer represented by aba is more preferable.

  In the thermoplastic elastomer (A), from the viewpoint of improving heat resistance and weather resistance, a part or all of the polymer block containing the conjugated diene compound is hydrogenated (hereinafter sometimes referred to as “hydrogenation”). It is preferable that The hydrogenation rate of the polymer block containing the conjugated diene compound at that time is preferably 80% or more, more preferably 90% or more. Here, in this specification, the hydrogenation rate is a value obtained by measuring the iodine value of the block copolymer before and after the hydrogenation reaction.

The content of the polymer block containing the aromatic vinyl compound unit in the thermoplastic elastomer (A) is preferably 5 to 75 mass with respect to the entire thermoplastic elastomer (A) from the viewpoint of flexibility and mechanical properties. %, More preferably, it is 5-60 mass%, More preferably, it is 10-40 mass%.
The weight average molecular weight of the thermoplastic elastomer (A) is preferably 30,000 to 500,000, more preferably 50,000 to 400,000, more preferably 60, from the viewpoints of mechanical properties and molding processability. 000 to 200,000, more preferably 70,000 to 200,000, particularly preferably 70,000 to 190,000, and most preferably 80,000 to 180,000. It is. Here, the weight average molecular weight is a polystyrene-reduced weight average molecular weight determined by gel permeation chromatography (GPC) measurement.
A thermoplastic elastomer (A) may be used individually by 1 type, and may be used in combination of 2 or more type. In particular, combining two types of medium molecular weight products with a weight average molecular weight of 50,000 to 150,000 and high molecular weight products with a weight average molecular weight of 150,000 to 300,000 will provide a better balance of mechanical properties, molding processability and adhesiveness. Since it becomes easy to take, it is preferable. For the same reason, when two kinds are combined, the medium molecular weight product / the high molecular weight product (mass ratio) is preferably 10/90 to 90/10, more preferably 20/80 to 75/25, and even more preferably. Is 20/80 to 55/45.

(Method for producing thermoplastic elastomer (A))
Although it does not specifically limit as a manufacturing method of a thermoplastic elastomer (A), For example, it can manufacture by an anionic polymerization method. In particular,
(I) a method of sequentially polymerizing the aromatic vinyl compound, the conjugated diene compound, and then the aromatic vinyl compound using an alkyl lithium compound as an initiator;
(Ii) a method in which an alkyl lithium compound is used as an initiator, the aromatic vinyl compound and the conjugated diene compound are sequentially polymerized, and then a coupling agent is added to perform coupling;
(Iii) A method of sequentially polymerizing the conjugated diene compound and then the aromatic vinyl compound using a dilithium compound as an initiator.

  Examples of the alkyl lithium compound in (i) and (ii) include methyl lithium, ethyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, pentyl lithium and the like. Examples of the coupling agent in (ii) include dichloromethane, dibromomethane, dichloroethane, dibromoethane, dibromobenzene and the like. Examples of the dilithium compound in (iii) include naphthalene dilithium and dilithiohexylbenzene.

The amounts of initiators and coupling agents such as these alkyllithium compounds and dilithium compounds are determined by the weight average molecular weight of the target thermoplastic elastomer (A), and the aromatic vinyl compound used in the anionic polymerization method and In general, 0.01 to 0.2 parts by mass of an initiator such as an alkyllithium compound and a dilithium compound are usually used for 100 parts by mass of the conjugated diene compound. In (ii), the coupling agent is usually used in an amount of 0.001 to 0.8 parts by mass with respect to 100 parts by mass in total of the aromatic vinyl compound and the conjugated diene compound used in the anionic polymerization method.
The anionic polymerization is preferably performed in the presence of a solvent. The solvent is not particularly limited as long as it is inert to the initiator and does not adversely affect the polymerization. For example, saturated aliphatic hydrocarbons such as hexane, heptane, octane, decane; toluene, benzene, xylene, etc. And aromatic hydrocarbons. Moreover, it is preferable to superpose | polymerize normally at 0-80 degreeC for 0.5 to 50 hours also by any above-mentioned method.

During the anionic polymerization, by adding an organic Lewis base, the amount of 1,2-bond and 3,4-bond of the thermoplastic elastomer (A) can be increased. The 1,2-bond amount and 3,4-bond amount of the thermoplastic elastomer (A) can be easily controlled.
Examples of the organic Lewis base include esters such as ethyl acetate; amines such as triethylamine, N, N, N ′, N′-tetramethylethylenediamine (TMEDA), and N-methylmorpholine; nitrogen-containing heterocyclic groups such as pyridine. Aromatic compounds; Amides such as dimethylacetamide; Ethers such as dimethyl ether, diethyl ether, tetrahydrofuran (THF) and dioxane; Glycol ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether; Sulphoxides such as dimethyl sulfoxide; Ketones such as acetone and methyl ethyl ketone Can be mentioned.

After the polymerization by the above method, the block copolymer contained in the reaction solution is solidified by pouring it into a poor solvent of the block copolymer such as methanol, or the reaction solution is poured into hot water together with steam. By removing the solvent by azeotropic distillation (steam stripping) and then drying, the unhydrogenated thermoplastic elastomer (A) can be isolated.
Furthermore, the hydrogenated thermoplastic elastomer (A) can be produced by subjecting the unhydrogenated thermoplastic elastomer (A) obtained above to a hydrogenation reaction. In the hydrogenation reaction, the unhydrogenated thermoplastic elastomer (A) obtained above is dissolved in a solvent inert to the reaction and the hydrogenation catalyst, or the unhydrogenated thermoplastic elastomer (A) is dissolved. Can be used as is without isolation from the reaction solution, and reacted with hydrogen in the presence of a hydrogenation catalyst.
Examples of the hydrogenation catalyst include Raney nickel; heterogeneous catalyst in which a metal such as Pt, Pd, Ru, Rh, Ni is supported on a carrier such as carbon, alumina, diatomaceous earth; transition metal compound, alkylaluminum compound, alkyllithium compound Ziegler catalysts composed of a combination with the above; metallocene catalysts and the like.
The hydrogenation reaction can usually be carried out under conditions of a hydrogen pressure of 0.1 to 20 MPa, a reaction temperature of 20 to 250 ° C., and a reaction time of 0.1 to 100 hours. In this method, the hydrogenation reaction liquid is poured into a poor solvent such as methanol to solidify, or the hydrogenation reaction liquid is poured into hot water together with steam and the solvent is removed azeotropically (steam stripping). By drying, the hydrogenated thermoplastic elastomer (A) can be isolated.

[Adhesion imparting component (B)]
The adhesion-imparting component (B) is for imparting adhesion to the thermoplastic polymer composition, and is usually used as a dispersed phase in the continuous phase (sea) of the thermoplastic elastomer (A) in the composition ( (Island-like) dispersed. This enables adhesion to both polar materials such as ceramics, metals and polar resins, and nonpolar materials such as polyolefins.

By the adhesion-imparting component (B), the film made of the thermoplastic polymer composition can be adhered well without applying an adhesive or applying a primer to the surface of an insert member such as ceramics, metal or synthetic resin. And a resin member can be insert-molded on the film.
The adhesion-imparting component (B) is preferably a polyvinyl acetal resin (B1) and / or a polar group-containing polypropylene resin (B2), and is a polyvinyl acetal resin (B1) and / or a carboxylic acid-modified polypropylene resin. It is more preferable.

(Polyvinyl acetal resin (B1))
The polyvinyl acetal resin (B1) imparts adhesiveness to the thermoplastic polymer composition, and is usually dispersed in islands in the composition. With the polyvinyl acetal (B1), the thermoplastic polymer composition can be satisfactorily adhered without subjecting the surface of the adherend such as ceramics, metal, or synthetic resin to a primer treatment.
The polyvinyl acetal resin (B1) usually has a repeating unit represented by the following formula (I).

In the above formula (I), n represents the number of types of aldehyde used in the acetalization reaction. _{R 1, R 2, ···,} R n represents an alkyl residue or a hydrogen atom of aldehyde used for the acetalization _{reaction, k (1), k (} 2), ···, k (n) is , Each represents a ratio (molar ratio) of structural units represented by []. L represents the proportion (molar ratio) of vinyl alcohol units, and m represents the proportion (molar ratio) of vinyl acetate units.
However, k ₍₁₎ + k ₍₂₎ +... + K _(n) + l + m = 1, and k ₍₁₎ , k ₍₂₎ ,..., K _(n) , l and m are any May be zero.
Each repeating unit is not particularly limited by the above-described arrangement order, and may be arranged at random, may be arranged in a block shape, or may be arranged in a taper shape.
The polyvinyl acetal resin (B1) is preferably polyvinyl butyral.

(Production method of polyvinyl acetal resin (B1))
The polyvinyl acetal resin (B1) can be obtained, for example, by reacting polyvinyl alcohol and an aldehyde.
The average degree of polymerization of the polyvinyl alcohol used for the production of the polyvinyl acetal resin (B1) is usually preferably 100 to 4,000, more preferably 100 to 3,000, still more preferably 100 to 2,000, particularly preferably. Is 250-2,000. When the average degree of polymerization of the polyvinyl alcohol is 100 or more, the production of the polyvinyl acetal resin (B1) is facilitated and the handleability is good. Moreover, when the average degree of polymerization of polyvinyl alcohol is 4,000 or less, the melt viscosity at the time of melt kneading does not become too high, and the production of the thermoplastic polymer composition is easy.
Here, the average degree of polymerization of polyvinyl alcohol is measured according to JIS K 6726. Specifically, it is a value determined from the intrinsic viscosity measured in 30 ° C. water after re-saponifying and purifying polyvinyl alcohol.

  The production method of polyvinyl alcohol is not particularly limited, and for example, a product produced by saponifying polyvinyl acetate or the like with alkali, acid, aqueous ammonia, or the like can be used. Moreover, you may use a commercial item. Examples of commercially available products include “Kuraray Poval” series manufactured by Kuraray Co., Ltd. Polyvinyl alcohol may be completely saponified or partially saponified. The saponification degree is preferably 80 mol% or more, more preferably 90 mol% or more, and further preferably 95 mol% or more.

  Moreover, as said polyvinyl alcohol, the copolymer of vinyl alcohol, such as an ethylene-vinyl alcohol copolymer and a partly saponified ethylene-vinyl alcohol copolymer, and the monomer copolymerizable with vinyl alcohol can be used. Furthermore, modified polyvinyl alcohol in which carboxylic acid or the like is partially introduced can be used. These polyvinyl alcohols may be used individually by 1 type, and may be used in combination of 2 or more type.

  The aldehyde used for production of the polyvinyl acetal resin (B1) is not particularly limited. For example, formaldehyde (including paraformaldehyde), acetaldehyde (including paraacetaldehyde), propionaldehyde, n-butyraldehyde, isobutyraldehyde, pentanal, hexanal, heptanal, n-octanal, 2-ethylhexylaldehyde, cyclohexanecarbaldehyde, furfural, Examples include glyoxal, glutaraldehyde, benzaldehyde, 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehyde, p-hydroxybenzaldehyde, m-hydroxybenzaldehyde, phenylacetaldehyde, β-phenylpropionaldehyde and the like. These aldehydes may be used individually by 1 type, and may be used in combination of 2 or more type. Of these aldehydes, butyraldehyde is preferred and n-butyraldehyde is more preferred from the viewpoint of ease of production.

The polyvinyl acetal resin (B1) obtained by acetalization using n-butyraldehyde is particularly referred to as polyvinyl butyral (PVB).
In the present invention, among the acetal units present in the polyvinyl acetal resin (B1), the proportion of butyral units (see the following formula) is preferably 0.8 or more, more preferably 0.9 or more, and still more preferably 0.8. 95 or more, particularly preferably substantially 1.
That is, in the structural formula of the polyvinyl acetal resin (B1) represented by the formula (I), when only R ₁ is nC ₃ H ₇ , 0.8 ≦ k ₍₁₎ / (k ₍₁₎ + k ₍₂₎ + ... + k _(n) ) is preferred.

The degree of acetalization of the polyvinyl acetal resin (B1) used in the present invention is preferably 55 to 88 mol%. The polyvinyl acetal resin (B1) having an acetalization degree of 55 mol% or more is low in production cost, easily available, and has good melt processability. On the other hand, the polyvinyl acetal resin (B1) having a degree of acetalization of 88 mol% or less is very easy to produce, and is economical because it does not require a long time for the acetalization reaction.
The degree of acetalization of the polyvinyl acetal resin (B1) is more preferably 60 to 88 mol%, further preferably 70 to 88 mol%, and particularly preferably 75 to 85 mol%. The lower the degree of acetalization of the polyvinyl acetal resin (B1), the larger the proportion of hydroxyl groups that the polyvinyl acetal resin (B1) has, which is advantageous in adhesiveness to ceramics, metals and synthetic resins. As a result, the affinity and compatibility with the thermoplastic elastomer (A) are improved, the mechanical properties of the thermoplastic polymer composition are excellent, and the adhesive strength with ceramics, metal and synthetic resin is increased.

The degree of acetalization (mol%) of the polyvinyl acetal resin (B1) is defined by the following formula.
Degree of acetalization (mol%) = {k ₍₁₎ + k ₍₂₎ +... + K _(n) } × 2 / {{k ₍₁₎ + k ₍₂₎ +... + K _(n) } × 2 + l + m } × 100
(In the above formula, n, k ₍₁₎ , k ₍₂₎ ,..., K _(n) , l and m are as defined above.)

The degree of acetalization of the polyvinyl acetal resin (B1) can be determined according to the method described in JIS K 6728 (1977). That is, the mass ratio of vinyl alcohol units (l ₀ ) and the mass ratio of vinyl acetate units (m ₀ ) are determined by titration, and the mass ratio of vinyl acetal units (k ₀ ) is calculated by k ₀ = 1−l ₀ −m ₀ . Ask. From this, the molar ratio l [l = (l ₀ /44.1)/(l ₀ /44.1+m ₀ /86.1+2k ₀ / Mw (acetal))] of vinyl alcohol units and the molar ratio m [m of vinyl acetate units = (M ₀ /86.1)/(l ₀ /44.1+m ₀ /86.1+k ₀ / Mw (acetal))], and the moles of the vinyl acetal unit according to the calculation formula of k = 1−1−m The ratio (k = k ₍₁₎ + k ₍₂₎ +... + K _(n) ) is obtained. Here, Mw (acetal) is a molecular weight per vinyl acetal unit. For example, in the case of polyvinyl butyral, Mw (acetal) = Mw (butyral) = 142.2. And {k ₍₁₎ + k ₍₂₎ +... + K _(n) } × 2 / {{k ₍₁₎ + k ₍₂₎ +... + K _(n) } × 2 + l + m} × 100 Can determine the degree of acetalization (mol%).
The degree of acetalization of the polyvinyl acetal resin (B1) was determined by dissolving the polyvinyl acetal resin (B1) in a suitable deuterated solvent such as deuterated dimethyl sulfoxide, and measuring ¹ H-NMR or ¹³ C-NMR. May be calculated.

  Further, as the polyvinyl acetal resin (B1), the vinyl alcohol unit is preferably 12 to 45 mol% (0.12 ≦ l ≦ 0.45), more preferably 12 to 40 mol% (0.12 ≦ l ≦ 0). 40), and preferably contains 0 to 5 mol% (0 ≦ m ≦ 0.05), more preferably 0 to 3 mol% (0 ≦ m ≦ 0.03) of vinyl acetate units.

The reaction (acetalization reaction) between polyvinyl alcohol and aldehyde can be performed by a known method. For example, an aqueous solution method in which an aqueous polyvinyl alcohol solution and an aldehyde are acetalized in the presence of an acid catalyst to precipitate particles of the polyvinyl acetal resin (B1); polyvinyl alcohol is dispersed in an organic solvent, Solvent method for precipitating polyvinyl acetal resin (B1) by acetalization reaction with aldehyde in the presence, and mixing the obtained reaction mixture with water, which is a poor solvent for polyvinyl acetal resin (B1). Etc.
The acid catalyst is not particularly limited, and examples thereof include organic acids such as acetic acid and p-toluenesulfonic acid; inorganic acids such as nitric acid, sulfuric acid and hydrochloric acid; gases which show acidity when an aqueous solution such as carbon dioxide is used; cation exchange Examples thereof include solid acid catalysts such as resins and metal oxides.

The slurry produced in the aqueous medium method or the solvent method is usually acidic by an acid catalyst. As a method for removing the acid catalyst, the slurry is repeatedly washed with water, and the pH is preferably adjusted to 5-9, more preferably 6-9, and even more preferably 6-8; a neutralizing agent is added to the slurry. A method of adjusting the pH to preferably 5 to 9, more preferably 6 to 9, and even more preferably 6 to 8; a method of adding alkylene oxides to the slurry, and the like.
Examples of the compound used for adjusting the pH include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal acetates such as sodium acetate; alkali metal such as sodium carbonate and potassium carbonate; Examples thereof include carbonates; alkali metal hydrogen carbonates such as sodium hydrogen carbonate; ammonia and aqueous ammonia solutions. Examples of the alkylene oxides include ethylene oxide, propylene oxide; glycidyl ethers such as ethylene glycol diglycidyl ether.

Next, salts generated by neutralization, aldehyde reaction residues, and the like are removed.
The removal method is not particularly limited, and methods such as repeated dehydration and water washing are usually used. The water-containing polyvinyl acetal resin (B1) from which residues and the like have been removed is dried as necessary and processed into powder, granules or pellets as necessary.
As the polyvinyl acetal resin (B1) used in the present invention, a resin obtained by reducing the aldehyde reaction residue, moisture, etc. by degassing under reduced pressure when processed into a powder, granule or pellet. .

  The thermoplastic polymer composition contains 10 to 100 parts by mass of the polyvinyl acetal resin (B1) with respect to 100 parts by mass of the thermoplastic elastomer (A). When the amount of the polyvinyl acetal resin (B1) is less than 10 parts by mass, it is difficult to obtain sufficient adhesion with ceramics, metal, and synthetic resin. More preferably, it is 12 mass parts or more, More preferably, it is 15 mass parts or more. On the other hand, when the amount of the polyvinyl acetal resin (B1) is more than 100 parts by mass, sufficient adhesiveness can be obtained, but the thermoplastic polymer composition becomes hard and the flexibility and mechanical properties are hardly exhibited. More preferably, it is 70 mass parts or less, More preferably, it is 50 mass parts or less, Most preferably, it is 45 mass parts or less. Accordingly, the content of the polyvinyl acetal resin (B1) is preferably 10 to 70 parts by mass, more preferably 12 to 70 parts by mass, and more preferably 15 to 70 parts with respect to 100 parts by mass of the thermoplastic elastomer (A). It is 15 mass parts, More preferably, it is 15-50 mass parts, Most preferably, it is 15-45 mass parts.

(Polar group-containing polypropylene resin (B2))
The polar group-containing polypropylene resin (B2) imparts adhesiveness to the thermoplastic polymer composition. By adding the polar group-containing polypropylene resin (B2) to the thermoplastic polymer composition, A film made of the plastic polymer composition can be satisfactorily bonded to an insert member made of ceramic, metal, synthetic resin or the like by a heat treatment at 190 ° C. or lower. Furthermore, even when an adhesive body formed by insert molding a resin member on the film bonded to the insert member is exposed to a temperature environment of 60 ° C. or higher, high adhesiveness is maintained.
Examples of the polar group contained in the polar group-containing polypropylene resin (B2) include (meth) acryloyloxy group; hydroxyl group; amide group; halogen atom such as chlorine atom; carboxyl group; acid anhydride group. Although there is no restriction | limiting in particular in the manufacturing method of this polar group containing polypropylene resin (B2), Propylene and a polar group containing copolymerizable monomer are random copolymerization, block copolymerization, or graft copolymerization by a well-known method. Obtained by. Among these, random copolymerization and graft copolymerization are preferable, and a graft copolymer is more preferable. In addition, it can also be obtained by subjecting a polypropylene resin to a reaction such as oxidation or chlorination by a known method.
The polar group-containing polypropylene resin (B2) may be obtained by copolymerizing an α-olefin other than propylene with a polar group-containing copolymerizable monomer together with propylene. Examples of the α-olefin include ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, cyclohexene and the like. The α-olefin can be copolymerized with a polar group-containing copolymerizable monomer by a known method, and examples thereof include random copolymerization, block copolymerization, and graft copolymerization. The proportion of structural units derived from α-olefins other than propylene to the total structural units of the polar group-containing polypropylene resin (B2) is preferably 0 to 45 mol%, more preferably 0 to 35 mol%, More preferably, it is 0-25 mol%.
Examples of the polar group-containing copolymerizable monomer include vinyl acetate, vinyl chloride, ethylene oxide, propylene oxide, acrylamide, unsaturated carboxylic acid, ester or anhydride thereof. Of these, unsaturated carboxylic acids or esters or anhydrides thereof are preferred. Examples of the unsaturated carboxylic acid or ester or anhydride thereof include (meth) acrylic acid, (meth) acrylic acid ester, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, highmic acid, and hymic anhydride. An acid etc. are mentioned. Of these, maleic acid and maleic anhydride are more preferable. These polar group-containing copolymerizable monomers may be used alone or in combination of two or more.
The polar group-containing polypropylene resin (B2) is preferably a polypropylene containing a carboxyl group as a polar group, that is, a carboxylic acid-modified polypropylene resin, from the viewpoint of adhesiveness. More preferred is a resin.

  Specific examples of the (meth) acrylic acid ester exemplified as the polar group-containing copolymerizable monomer include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, and n-butyl acrylate. , Alkyl acrylates such as isobutyl acrylate, n-hexyl acrylate, isohexyl acrylate, n-octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate Methacrylic acid such as isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, isohexyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, 2-ethylhexyl methacrylate They include alkyl esters. These (meth) acrylic acid esters may be used alone or in combination of two or more.

  The polar group of the polar group-containing polypropylene resin (B2) may be post-treated after polymerization. For example, it may be neutralized with a metal ion of a (meth) acrylic acid group or a carboxyl group to form an ionomer, or may be esterified with methanol or ethanol. Further, hydrolysis of vinyl acetate or the like may be performed.

The melt flow rate (MFR) of the polar group-containing polypropylene-based resin (B2) under the conditions of 230 ° C. and a load of 2.16 kg (21.18 N) is preferably 0.1 to 300 g / 10 minutes, more preferably 0.8. 1-100 g / 10 minutes, more preferably 0.1-70 g / 10 minutes, more preferably 0.1-50 g / 10 minutes, more preferably 1-30 g / 10 minutes, still more preferably 1-20 g / 10 minutes Particularly preferably, it is 1 to 15 g / 10 min. If the MFR of the polar group-containing polypropylene resin (B2) under the above conditions is 0.1 g / 10 min or more, good moldability can be obtained. On the other hand, if the MFR is 300 g / 10 min or less, the mechanical characteristics are easily developed.
The melting point of the polar group-containing polypropylene resin (B2) is preferably 100 ° C. or higher, more preferably 110 to 170 ° C., and further preferably 120 to 145 ° C., from the viewpoint of heat resistance.

  The ratio of the polar group-containing structural unit of the polar group-containing polypropylene resin (B2) to the total structural unit of the polar group-containing polypropylene resin (B2) is preferably 0.01 to 10% by mass. If it is 0.01 mass% or more, the adhesiveness with respect to an insert member and a resin member will become high. If the ratio of a polar group containing structural unit is 10 mass% or less, affinity with a thermoplastic elastomer (A) will improve, a mechanical characteristic will become favorable, and the production | generation of a gel will also be suppressed. From the same viewpoint, the ratio is preferably 0.01 to 7% by mass, more preferably 0.01 to 5% by mass, more preferably 0.1 to 3% by mass, and still more preferably 0.2 to 1% by mass. %. You may use what diluted the polypropylene resin which has a polar group containing structural unit in high concentration with the polypropylene resin which does not have a polar group containing structural unit so that the ratio of a polar group containing structural unit may become the optimal.

The thermoplastic polymer composition contains 10 to 100 parts by mass of the polar group-containing polypropylene resin (B2) with respect to 100 parts by mass of the thermoplastic elastomer (A). When the polar group-containing polypropylene resin (B2) is less than 10 parts by mass, it is difficult to adhere to the insert member and the resin member. On the other hand, when the amount of the polar group-containing polypropylene resin (B2) is more than 100 parts by mass, sufficient adhesiveness can be obtained, but the thermoplastic polymer composition becomes hard and flexibility and mechanical properties are hardly exhibited. From the same viewpoint, the content of the polar group-containing polypropylene resin (B2) is preferably 12 parts by mass or more, more preferably 15 parts by mass or more, preferably 100 parts by mass of the thermoplastic elastomer (A). Is 70 parts by mass or less, more preferably 50 parts by mass or less.
Accordingly, the content of the polar group-containing polypropylene resin (B2) is preferably 15 to 70 parts by mass, more preferably 15 to 50 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer (A).

[Compatibilizer (C)]
The thermoplastic polymer composition further includes a polar group-containing polyolefin copolymer (except the polar group-containing polypropylene resin (B2)) (C1), and a polymer block containing an aromatic vinyl compound unit; A block copolymer having a polymer block containing a conjugated diene compound unit or a hydrogenated product thereof, containing a compatibilizer (C) selected from thermoplastic elastomers (C2) having a polar group Is preferred.
By including the compatibilizing agent (C) in the thermoplastic polymer composition, molding processability is improved, and a film made of the thermoplastic polymer composition is easily produced. In addition, the mechanical properties of the film are improved and handling becomes easy. Furthermore, it can adhere | attach with an insert member favorably also by heat processing at 190 degrees C or less.
Although such details are not necessarily clear in detail, it is considered that each component is in a dispersed state in the thermoplastic polymer composition. The adhesion-imparting component (B) is also distributed on the surface of the composition, and the compatibilizer (C) has a high binding force with both the thermoplastic elastomer (A) and the adhesion-imparting component (B), and at the time of peeling. Since no breakage occurs at the boundary between the components, it is presumed that the effects specific to the present invention appear.

(Polar group-containing polyolefin copolymer (C1))
Examples of the polar group of the polar group-containing polyolefin copolymer (C1) include an ester group, a hydroxyl group, a carboxyl group, an acid anhydride group, an amide group, and a halogen atom such as a chlorine atom.
As the polar group-containing polyolefin copolymer (C1), a polyolefin copolymer comprising an olefin copolymerizable monomer and a polar group-containing copolymerizable monomer is preferable.
The polyolefin copolymer is obtained by copolymerizing an olefin copolymerizable monomer and a polar group-containing copolymerizable monomer.
Examples of the olefin copolymerizable monomer include ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, and cyclohexene. These olefin copolymerizable monomers may be used individually by 1 type, and may combine 2 or more types. Among these, ethylene is more preferable.
Examples of the polar group-containing copolymerizable monomer include (meth) acrylic acid ester, (meth) acrylic acid, vinyl acetate, vinyl chloride, ethylene oxide, propylene oxide, and acrylamide. These polar group-containing copolymerizable monomers may be used alone or in combination of two or more. Of these, (meth) acrylic acid esters are preferred.

  Specific examples of the (meth) acrylic acid ester preferable as the polar group-containing copolymerizable monomer include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, and n-butyl acrylate. , Alkyl acrylates such as isobutyl acrylate, n-hexyl acrylate, isohexyl acrylate, n-octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate Methacrylic acid, such as isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, isohexyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, 2-ethylhexyl methacrylate Acid alkyl esters. These (meth) acrylic acid esters may be used alone or in combination of two or more. Among these, alkyl acrylate is preferable, methyl acrylate and ethyl acrylate are more preferable, and methyl acrylate is more preferable from the viewpoint of obtaining high adhesiveness by heat treatment at 190 ° C. or lower.

The polymerization form of the polar group-containing polyolefin copolymer (C1) used in the present invention is not particularly limited, and a random copolymer, a block copolymer, or the like can be used. Among these, a random copolymer is preferable.
The polar group of the polar group-containing polyolefin copolymer (C1) used in the present invention may be post-treated after polymerization. For example, neutralization with a metal ion of (meth) acrylic acid may be performed to obtain an ionomer, or hydrolysis of vinyl acetate may be performed.

  The melt flow rate (MFR) of the polar group-containing polyolefin copolymer (C1) used in the present invention under conditions of 190 ° C. and a load of 2.16 kg (21.18 N) is preferably 0.1 to 100 g / 10. Min, more preferably 0.1 to 70 g / 10 min, more preferably 0.1 to 50 g / 10 min, more preferably 1 to 30 g / 10 min, still more preferably 1 to 20 g / 10 min, particularly preferably 1 -10 g / 10 min. If the MFR of the polar group-containing olefin copolymer (C1) under the above conditions is 0.1 g / 10 min or more, sufficient adhesive strength can be obtained even by heat treatment at 190 ° C. or less. On the other hand, when the MFR is 100 g / 10 min or less, it is easy to obtain and mechanical characteristics are easily developed.

  The Vicat softening point of the polar group-containing polyolefin copolymer (C1) used in the present invention is preferably 40 to 100 ° C, more preferably 45 to 95 ° C, more preferably 45 to 75 ° C, and still more preferably 45 to 75 ° C. 65 ° C., particularly preferably 45 to 55 ° C. If the Vicat softening point of the polar group-containing polyolefin copolymer (C1) is 40 ° C. or higher, the mechanical properties of the thermoplastic polymer composition will be good. In addition, when the Vicat softening point is 100 ° C. or lower, the adhesive strength is increased even by heat treatment at 190 ° C. or lower.

The ratio of the polar group-containing structural unit of the polar group-containing polyolefin copolymer (C1) to the total structural unit of the polar group-containing polyolefin copolymer (C1) is preferably 1 to 99% by mass, more preferably. Is 1 to 50% by mass, more preferably 1 to 40% by mass, and particularly preferably 5 to 30% by mass. If the ratio of the polar group-containing structural unit is within this range, the affinity and compatibility with the thermoplastic elastomer (A) and the compatibility and compatibility with the adhesion-imparting component (B) are good. The mechanical properties of the combined composition are improved, the adhesiveness to the insert member and the resin member is increased, and it can be bonded to the insert member even by heat treatment at 190 ° C. or lower.
As the proportion of the polar group-containing structural unit decreases, the mechanical properties of the thermoplastic polymer composition tend to decrease, and as the proportion of the polar group-containing structural unit increases, the thermoplastic elastomer (A ) And the compatibility tend to be low.

The thermoplastic polymer composition preferably contains 5 to 100 parts by mass of the polar group-containing polyolefin copolymer (C1) with respect to 100 parts by mass of the thermoplastic elastomer (A). If the polar group-containing polyolefin copolymer (C1) is less than 5 parts by mass, it may be difficult to bond the insert member and the resin member by heat treatment at 190 ° C. or lower. On the other hand, when the polar group-containing polyolefin-based copolymer (C1) is more than 100 parts by mass, sufficient adhesiveness can be obtained, but the thermoplastic polymer composition becomes hard and flexibility and mechanical properties are hardly exhibited. Sometimes. The content of the polar group-containing polyolefin copolymer (C1) is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and further preferably 35 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer (A). It is above, More preferably, it is 70 mass parts or less, More preferably, it is 60 mass parts or less.
From these, the content of the polar group-containing polyolefin copolymer (C1) is preferably 5 to 70 parts by mass, more preferably 10 to 70 parts by mass, and more preferably 10 to 70 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer (A). Preferably it is 20-70 mass parts, Most preferably, it is 35-60 mass parts.

(A block copolymer having a polymer block containing an aromatic vinyl compound unit and a polymer block containing a conjugated diene compound unit or a hydrogenated product thereof, and a thermoplastic elastomer having a polar group (C2))
A block copolymer having a polymer block containing an aromatic vinyl compound unit and a polymer block containing a conjugated diene compound unit used in the present invention or a hydrogenated product thereof, and a thermoplastic elastomer having a polar group ( C2) (hereinafter may be abbreviated as “a thermoplastic elastomer having a polar group (C2)”) includes at least one polymer block (c2-1) containing an aromatic vinyl compound unit, hydrogen It consists of at least one polymer block (c2-2) containing a conjugated diene compound unit and at least one polymer block (c2-3) having a polar functional group. The content of the polymer block (c2-1) in the thermoplastic elastomer (C2) having a polar group is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and still more preferably 15 to 35% by mass. Especially preferably, it is 20-35 mass%.
In the present specification, the content of the polymer block (c2-1) in the thermoplastic elastomer (C2) having a polar group is a value determined by nuclear magnetic resonance spectroscopy ( ¹ H-NMR).

  Examples of the aromatic vinyl compound constituting the polymer block (c2-1) of the thermoplastic elastomer (C2) having the polar group include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4- Examples thereof include methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, 1-vinylnaphthalene, 2-vinylnaphthalene and the like. Among these, styrene, α-methylstyrene, and 4-methylstyrene are preferable. Each of the polymer blocks (c2-1) may contain only one type of structural unit derived from these aromatic vinyl compounds, or may contain a structural unit derived from two or more types.

  Moreover, the said polymer block (c2-1) may contain the other polymerizable monomer unit, unless the effect of this invention is reduced remarkably. Examples of the other polymerizable monomer include conjugated diene compounds such as butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and 1,3-hexadiene. The content of the aromatic vinyl compound unit in the polymer block (c2-1) is preferably 70% by mass or more, more preferably 80% by mass or more, and more preferably 90% by mass or more. The content is more preferably 95% by mass or more, and particularly preferably substantially 100% by mass.

Examples of the conjugated diene compound constituting the polymer block (c2-2) containing a conjugated diene compound unit, which is hydrogenated from the thermoplastic elastomer (C2) having a polar group, include butadiene, isoprene, 2, 3 -Dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene and the like. The polymer block (c2-2) may be composed only of structural units derived from one of these conjugated diene compounds, or may be composed of structural units derived from two or more types. . Among these, the conjugated diene compound constituting the polymer block (c2-2) is preferably one or both of isoprene and butadiene.
When the polymer block (c2-2) is composed of two or more conjugated diene compounds such as butadiene and isoprene, the mixing ratio and polymerization form (block, random, etc.) are not particularly limited. When the polymer block (c2-2) is composed of butadiene and isoprene, the mixing molar ratio of butadiene and isoprene is not particularly limited, but from the viewpoint of balance between mechanical properties and flexibility, butadiene / isoprene = It is preferably 10/90 to 90/10, more preferably 30/70 to 70/30, still more preferably 40/60 to 60/40, and 40/60 to 50/50. It is particularly preferred.

  The bonding form of the conjugated diene compound constituting the polymer block (c2-2) containing the conjugated diene compound unit, which is hydrogenated from the thermoplastic elastomer (C2) having a polar group, is not particularly limited. For example, in the case of butadiene, 1,2-bond and / or 1,4-bond, and in the case of isoprene, one of 1,2-bond, 3,4-bond and 1,4-bond The above can be taken. Among these, when the polymer block (c2-2) is mainly composed of butadiene, mainly composed of isoprene, or mainly composed of both isoprene and butadiene, the polymer block (c2) -2) is preferably 1 to 95 mol%, more preferably 1 to 70 mol%, and more preferably 1 to 45 mol%. Further preferred.

  The polymer block (c2-2) may contain other polymerizable monomer as long as the effect of the present invention is not significantly reduced. Examples of other polymerizable monomers include styrene, α-methylstyrene, 4-methylstyrene, and the like. In any of the polymer blocks (c2-2), the content of the conjugated diene compound unit is preferably 70% by mass or more, more preferably 80% by mass or more, and 90% by mass or more. More preferably, it is more preferably 95% by mass or more, and particularly preferably substantially 100% by mass.

  The polymer block (c2-2) containing the conjugated diene compound unit of the thermoplastic elastomer (C2) having a polar group may be hydrogenated (hydrogenated). The hydrogenation rate of the carbon-carbon double bond derived from the conjugated diene compound unit contained in the polymer block (c2-2) is preferably 80% or more, and more preferably 90% or more.

  The bonding form of the polymer block (c2-1) and the polymer block (c2-2) in the thermoplastic elastomer (C2) having a polar group is linear, branched, radial, or a combination of two or more of these. However, it is preferably a linear bond form. When the polymer block (c2-1) is represented by “A” and the polymer block (c2-2) is represented by “B”, for example, an “AB” type diblock copolymer, “A- "B-A" type or "B-A-B" type triblock copolymer, "A-B-A-B" type tetrablock copolymer, "B-A-B-A-B" type , "A-B-A-B-A" type pentablock copolymer, "(A-B) nX" type copolymer (X represents a coupling agent residue, n represents an integer of 2 or more And a mixture thereof. Among these, a triblock copolymer is preferable, and an “ABA” type triblock copolymer is more preferable.

The polymer block (c2-3) is a polymer block having a polar functional group, for example, a condensation block such as a polyester block, a polyamide block, a polyurethane block, a polycarbonate block, a polyurea block, or a polyacetal block. Polymer block: vinyl such as polyvinyl alcohol, polyvinyl acetal, ethylene-vinyl alcohol copolymer, polyvinyl acetate, ethylene-vinyl acetate copolymer, propylene-vinyl alcohol copolymer, polyhydroxystyrene, sulfonated polystyrene, polyvinylpyridine Polymer block: poly (meth) acrylate, poly (meth) ethyl acrylate, poly (meth) acrylate, isopropyl poly (meth) acrylate, poly (meth) acrylate n Butyl, sec-butyl poly (meth) acrylate, tert-butyl poly (meth) acrylate, pentyl poly (meth) acrylate, hexyl poly (meth) acrylate, octyl poly (meth) acrylate, poly (meth) 2-ethylhexyl acrylate, poly (meth) acrylate dodecyl, poly (meth) acrylate myristyl, poly (meth) acrylate palmitate, poly (meth) acrylate stearyl, poly (meth) acrylate behenyl, poly (meth) Acrylics such as cyclohexyl acrylate, poly (meth) acrylate phenyl, poly (meth) hydroxymethyl hydroxy, poly (meth) hydroxyethyl hydroxy, poly (meth) acrylic hydroxyethoxyethyl, poly (meth) acrylic acid, etc. Polymer block and two or more acrylics Copolymer system monomers; copolymerized ethylene copolymer acrylic polymer block further monomer and ethylenic monomer constituting the acrylic polymer; and polyketone and polyethylene oxide, such as addition polymerized polymer block can be given.
Especially, it is preferable that a polymer block (c2-3) is a polyurethane-type block from viewpoints, such as compatibility with an adhesion | attachment provision component (B).

(Method for producing thermoplastic elastomer (C2) having a polar group)
Although there is no restriction | limiting in particular in the manufacturing method of the thermoplastic elastomer (C2) which has a polar group, For example, the thermoplastic polyurethane elastomer used as the polyurethane-type block as a polymer block (c2-3), and the said polymer block (c2- A terminal-modified hydrogenated block copolymer (x) having at least one of 1) and at least one of the polymer blocks (c2-2) and having a functional group (preferably a hydroxyl group) at a terminal; A method of kneading and reacting under melting conditions is preferred. From the reaction product thus obtained, the desired thermoplastic elastomer (C2) having a polar group can be isolated by a known method.
The melt kneading of the thermoplastic polyurethane elastomer and the terminal-modified hydrogenated block copolymer (x) can be performed using a known melt kneading apparatus such as a single screw extruder, a twin screw extruder, a kneader, or a Banbury mixer. . The melt-kneading conditions can be selected according to the type of thermoplastic polyurethane elastomer and terminal-modified hydrogenated block copolymer (x) to be used, the type of apparatus, etc., but generally at a temperature of 180 to 250 ° C. For about 1 to 15 minutes.
Here, the melt viscosity of the thermoplastic elastomer (C2) having a polar group is 1 to 30 kPa · s from the viewpoint that the obtained thermoplastic polymer composition has better mechanical properties and adhesiveness. Preferably, it is 3-20 kPa * s. And the terminal modified hydrogenated block copolymer (x) which comprises the thermoplastic elastomer (C2) which has a polar group from the point which the moldability of the thermoplastic polymer composition obtained and a coloring prevention property become more favorable. ) Are preferably 30,000 to 300,000, respectively. More preferably, it is 40,000-250,000.

In addition, the thermoplastic elastomer (C2) having the above polar group is, for example, a terminal-modified hydrogenated block copolymer (in the reaction system at the beginning or during the reaction when producing a thermoplastic polyurethane elastomer). It can also be obtained by adding x) and reacting, followed by isolation by known methods.
That is, the unreacted thermoplastic polyurethane elastomer in the obtained thermoplastic elastomer (C2) having a polar group can be removed by extracting the obtained reaction mixture with dimethylformamide or the like. Subsequently, the unreacted terminal-modified hydrogenated block copolymer (x) can be removed by extraction from the reaction mixture using cyclohexane or the like, and the thermoplastic elastomer (C2) having a polar group as the target product. Can be isolated. The thermoplastic elastomer (C2) having the polar group includes an unreacted thermoplastic polyurethane elastomer and an unreacted terminal-modified hydrogenated block copolymer (x) derived from the production method described above. It may be.

The thermoplastic polyurethane elastomer can be obtained, for example, by kneading and reacting a polymer diol, an organic diisocyanate and a chain extender in an extruder or the like.
Examples of the polymer diol include polyether polyol and polyester polyol.
Examples of the polyether polyol include polyether diols and glycols (for example, ethylene glycol, propylene glycol, 1,4- Butanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, etc. And polyether polyols obtained by polycondensation.

  Examples of the polyester polyol include polyester polyols obtained by a known polycondensation method using an esterification method or a transesterification method using a polycarboxylic acid, a polyol, and other components as required. As the polyol, those generally used in the production of polyester can be used. For example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 2-methyl-1,3- Propanediol, 2,2-diethyl-1,3-propanediol, 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 2- Methyl-1,8-octanediol, 2,7-dimethyl-1,8-octanediol, 1,9-nonanediol, 2-methyl-1,9-nonanediol, 2,8-dimethyl-1,9- C2-C15 aliphatic diol such as nonanediol; 1,4-cyclohexanediol, cyclo Diols having two hydroxyl groups per molecule, such as alicyclic diols such as xanthanimethanol and cyclooctanedimethanol; aromatic dihydric alcohols such as 1,4-bis (β-hydroxyethoxy) benzene, and trimethylolpropane; Examples thereof include a polyol having 3 or more hydroxyl groups per molecule such as trimethylolethane, glycerin, 1,2,6-hexanetriol, pentaerythritol, diglycerin and the like. As the polycarboxylic acid, polycarboxylic acids generally used in the production of polyesters can be used. For example, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanediate. C4-C12 aliphatic dicarboxylic acids such as acid, methylsuccinic acid, 2-methylglutaric acid, and trimethyladipic acid; cycloaliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid, dimer acid, and hydrogenated dimer acid; terephthalic acid, isophthalic acid Examples thereof include aromatic dicarboxylic acids such as acid, orthophthalic acid and naphthalenedicarboxylic acid; trifunctional or higher polycarboxylic acids such as trimellitic acid and pyromellitic acid.

Examples of the organic diisocyanate include aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMDI), and lysine diisocyanate (LDI); cyclohexane 1,4-diisocyanate, isophorone diisocyanate (IPDI), water Aliphatic diisocyanates such as hydrogenated xylylene diisocyanate and hydrogenated bis (isocyanatophenyl) methane; phenylene diisocyanate, tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), naphthalene diisocyanate ( NDI), bis (isocyanatophenyl) methane (MDI), toluidine diisocyanate Over preparative (TODI), and aromatic diisocyanates such as 1,3-bis (isocyanatomethyl phenyl) propane.
As the chain extender, for example, any chain extender used in the production of ordinary thermoplastic polyurethanes may be used, and the molecular weight having two or more active hydrogen atoms capable of reacting with an isocyanate group in the molecule. It is preferable to use a low molecular compound of 300 or less. Examples of the low molecular weight compound include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-bis (β-hydroxyethoxy) benzene, 1,4-cyclohexanediol, bis ( (β-hydroxyethyl) aliphatic or alicyclic diols such as terephthalate and xylylene glycol; diamines such as ethylenediamine, propylenediamine, xylylenediamine, isophoronediamine, piperazine and derivatives thereof, phenylenediamine, tolylenediamine, xylenediamine; Examples include amino alcohols such as aminoethyl alcohol and aminopropyl alcohol.

Moreover, said terminal modified hydrogenated block copolymer (x) can be produced by a conventionally known method. For example, after forming a molecular chain of a block copolymer by an ion polymerization method such as anionic polymerization or cationic polymerization, a single site polymerization method, a living radical method, etc., a hydroxyl group is added to the terminal of the molecular chain, and a known method Can be produced by hydrogenation.
For example, in the case of anionic polymerization, an aromatic vinyl compound and a conjugated diene compound are sequentially polymerized in an inert organic solvent such as n-hexane or cyclohexane using an alkyl lithium compound as a polymerization initiator to obtain a desired molecule. When the structure and molecular weight are reached, compounds with an oxirane skeleton such as ethylene oxide, propylene oxide, styrene oxide, or lactone compounds such as ε-caprolactone, β-propiolactone, dimethylpropiolactone (pivalolactone), etc. A block copolymer having a hydroxyl group at one end can be produced by addition and then adding an active hydrogen compound such as alcohols, carboxylic acids and water to stop the polymerization. The average hydroxyl value is used as a guide for the number of hydroxyl groups per molecule of the block copolymer. The average hydroxyl value is preferably 0.5 or more, and more preferably 0.7 or more.
Note that the average hydroxyl value in the present specification, calculated from integrated value of the ^{1 H-NMR} are obtained from the measurement, hydrogen atoms bonded to the carbon adjacent to terminal hydroxyl group of the terminal-modified hydrogenated block copolymer (x) It means the ratio of the number of moles of the terminal hydroxyl group to the number of moles of the initiator terminal calculated from the integrated value of hydrogen atoms derived from the initiator terminal.

  Next, the terminal-modified hydrogenated block copolymer (x) can be obtained by subjecting the block copolymer having a hydroxyl group at one end to the hydrogenation reaction obtained above. In the hydrogenation reaction, the block copolymer having a hydroxyl group at one end obtained above is dissolved in a solvent inert to the reaction and the hydrogenation catalyst, or a hydroxyl group is added at one end obtained above. The block copolymer is not isolated from the polymerization reaction solution containing the block copolymer having, and the polymerization reaction solution can be used as it is and reacted with hydrogen in the presence of the same hydrogenation catalyst as described above. . The hydrogenation reaction is usually carried out under conditions of a hydrogen pressure of 0.1 to 20 MPa, a reaction temperature of 20 to 250 ° C., and a reaction time of 0.1 to 100 hours. The reaction mixture obtained by the hydrogenation reaction was poured into a poor solvent such as methanol to solidify, or the hydrogenation reaction liquid was poured into hot water together with steam to remove the solvent by azeotropic distillation (steam stripping). Thereafter, the terminal-modified hydrogenated block copolymer (x) can be obtained by drying. The terminal-modified hydrogenated block copolymer (x) may include a hydrogenated block copolymer having no functional group at the terminal derived from the above-described production method. It can be used as a raw material for producing a thermoplastic elastomer (C2) having a polar group. Such a hydrogenated block copolymer having no functional group at the terminal does not participate in the production reaction of the thermoplastic elastomer (C2) having a polar group, and as described above, the thermoplastic elastomer (C2 having a polar group). ) In the process of isolating.

  The thermoplastic polymer composition preferably contains 0.1 to 20 parts by mass of the thermoplastic elastomer (C2) having a polar group with respect to 100 parts by mass of the thermoplastic elastomer (A). When the thermoplastic elastomer (C2) having a polar group is less than 0.1 part by mass, it may be difficult to obtain the adhesiveness of the thermoplastic polymer composition. Although the detailed reason is not clear, if the thermoplastic elastomer (C2) having a polar group is too little due to low compatibility between the thermoplastic elastomer (A) and the adhesion-imparting component (B), the thermoplastic polymer It has been estimated that problems such as formation of a skin layer near the surface of the molded article made of the composition and delamination of the molded article may occur. For this reason, the content of the thermoplastic elastomer (C2) having a polar group is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more with respect to 100 parts by mass of the thermoplastic elastomer (A). On the other hand, when the thermoplastic elastomer (C2) having a polar group is more than 20 parts by mass, mechanical properties, anti-coloring properties, and moldability may be inferior. For this reason, content of the thermoplastic elastomer (C2) which has a polar group becomes like this. Preferably it is 17 mass parts or less with respect to 100 mass parts of thermoplastic elastomers (A), More preferably, it is 15 mass parts or less. From the above, the content of the thermoplastic elastomer (C2) having a polar group is preferably 0.5 to 20 parts by mass, more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer (A). More preferably, it is 1-17 mass parts, Most preferably, it is 1-15 mass parts.

(Tackifying resin (D))
The thermoplastic polymer composition may further contain a tackifying resin (D) as necessary. By including the tackifier resin (D), the moldability is further improved while maintaining the adhesive properties.
Examples of the tackifying resin (D) include aliphatic unsaturated hydrocarbon resins, aliphatic saturated hydrocarbon resins, alicyclic unsaturated hydrocarbon resins, alicyclic saturated hydrocarbon resins, aromatic hydrocarbon resins, water Hydrogenated aromatic hydrocarbon resin, rosin ester resin, hydrogenated rosin ester resin, terpene phenol resin, hydrogenated terpene phenol resin, terpene resin, hydrogenated terpene resin, aromatic hydrocarbon modified terpene resin, coumarone / indene resin, phenol resin And xylene resin. Tackifying resin (D) may be used individually by 1 type, and may be used in combination of 2 or more type. Among these, aliphatic saturated hydrocarbon resins, alicyclic saturated hydrocarbon resins, hydrogenated aromatic hydrocarbon resins, and hydrogenated terpene resins are preferable, and hydrogenated aromatic hydrocarbon resins and hydrogenated terpene resins are more preferable.

The softening point of the tackifier resin (D) is preferably 50 to 200 ° C, more preferably 65 to 180 ° C, and still more preferably 80 to 160 ° C. If the softening point is 50 ° C. or higher, the adhesive property with respect to the environmental temperature can be maintained. On the other hand, if the softening point is 200 ° C. or lower, the adhesive properties with respect to the heat treatment temperature can be maintained.
Here, the softening point is a value measured according to ASTM 28-67.

  When the tackifier resin (D) is contained in the thermoplastic polymer composition, the content thereof is preferably 1 to 100 parts by mass, more preferably 5 to 70 parts per 100 parts by mass of the thermoplastic elastomer (A). It is 5 mass parts, More preferably, it is 5-50 mass parts, Most preferably, it is 10-45 mass parts. If the content of the tackifier resin (D) is 100 parts by mass or less with respect to 100 parts by mass of the thermoplastic elastomer (A), the thermoplastic polymer composition does not become hard, and flexibility and mechanical properties are easily exhibited. .

(Softener (E))
The thermoplastic polymer composition may further contain a softener (E) as necessary. Examples of the softener (E) include softeners generally used for rubber and plastics.
For example, paraffinic, naphthenic and aromatic process oils; phthalic acid derivatives such as dioctyl phthalate and dibutyl phthalate; white oil, mineral oil, ethylene and α-olefin oligomers, paraffin wax, liquid paraffin, polybutene, low molecular weight polybutadiene And low molecular weight polyisoprene. Among these, process oil is preferable, and paraffinic process oil is more preferable.
Also, known softeners generally used in combination with polyvinyl acetal resins, for example, organic acid ester plasticizers such as monobasic organic acid esters and polybasic organic acid esters; organic phosphate esters, organic phosphorus Phosphoric plasticizers such as acid esters can also be used.
Examples of the basic organic acid ester include triethylene glycol-dicaproic acid ester, triethylene glycol-di-2-ethylbutyric acid ester, triethylene glycol-di-n-octylic acid ester, triethylene glycol-di-2-ethylhexyl. Glycols such as triethylene glycol, tetraethylene glycol, and tripropylene glycol typified by acid esters, butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptylic acid, n-octylic acid, 2-ethylhexylic acid, pelargon Examples thereof include glycol esters obtained by reaction with monobasic organic acids such as acid (n-nonyl acid) and decyl acid.
Examples of the polybasic acid organic esters include polybasic organic acids such as adipic acid, sebacic acid, azelaic acid, and the like, such as sebacic acid dibutyl ester, azelaic acid dioctyl ester, adipic acid dibutyl carbitol ester, and the like. Examples include esters.
Examples of the organic phosphate ester include tributoxyethyl phosphate, isodecylphenyl phosphate, triisopropyl phosphate, and the like.
A softener (E) may be used individually by 1 type, and may be used in combination of 2 or more type.

  The thermoplastic polymer composition is preferably 0.1 to 300 parts by mass of the softening agent (E) with respect to 100 parts by mass of the thermoplastic elastomer (A), if necessary, from the viewpoint of moldability and adhesiveness. Parts, more preferably 1 to 200 parts by weight, more preferably 10 to 200 parts by weight, further preferably 50 to 200 parts by weight, and particularly preferably 50 to 150 parts by weight.

(Other optional ingredients)
The thermoplastic polymer composition contains other thermoplastic polymers such as an olefin polymer, a styrene polymer, a polyphenylene ether resin, and polyethylene glycol as necessary, as long as the effects of the present invention are not significantly impaired. You may do it. Examples of the olefin polymer include polyethylene, polypropylene, polybutene, block copolymers of propylene and other α-olefins such as ethylene and 1-butene, and random copolymers.
When other thermoplastic polymer is contained, the content thereof is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, more preferably 20 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer (A). Hereinafter, it is further preferably 10 parts by mass or less, particularly preferably 5 parts by mass or less.

The thermoplastic polymer composition may contain an inorganic filler as necessary. The inorganic filler is useful for improving the physical properties such as heat resistance and weather resistance of the thermoplastic polymer composition, adjusting the hardness, and improving the economical efficiency as an extender. Examples of the inorganic filler include calcium carbonate, talc, magnesium hydroxide, aluminum hydroxide, mica, clay, natural silicic acid, synthetic silicic acid, titanium oxide, carbon black, barium sulfate, glass balloon, and glass fiber. It is done. An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type.
When the inorganic filler is contained, the content thereof is preferably within a range in which the flexibility of the thermoplastic polymer composition is not impaired, and is generally preferably 100 with respect to 100 parts by mass of the thermoplastic elastomer (A). It is not more than part by mass, more preferably not more than 70 parts by mass, still more preferably not more than 30 parts by mass, particularly preferably not more than 10 parts by mass.

The thermoplastic polymer composition is an antioxidant, a lubricant, a light stabilizer, a processing aid, a colorant such as a pigment or a dye, a flame retardant, an antistatic agent, as long as the effect of the invention is not impaired. It may contain a matting agent, silicone oil, an antiblocking agent, an ultraviolet absorber, a release agent, a foaming agent, an antibacterial agent, an antifungal agent, a fragrance and the like.
Examples of the antioxidant include hindered phenol-based, phosphorus-based, lactone-based, and hydroxyl-based antioxidants. Among these, hindered phenol antioxidants are preferable. When the antioxidant is contained, the content thereof is preferably in a range not colored when the resulting thermoplastic polymer composition is melt-kneaded, and preferably with respect to 100 parts by mass of the thermoplastic elastomer (A). Is 0.1 to 5 parts by mass.

  The method for preparing the thermoplastic polymer composition is not particularly limited, and any method can be used as long as the above components can be mixed uniformly. Usually, a melt-kneading method is used. Melt-kneading can be performed using, for example, a melt-kneading apparatus such as a single-screw extruder, a twin-screw extruder, a kneader, a batch mixer, a roller, or a Banbury mixer. As a result, a thermoplastic polymer composition can be obtained.

  The thermoplastic polymer composition thus obtained has a hardness according to the JIS-A method of JIS K 6253 (hereinafter sometimes referred to as “A hardness”), preferably 90 or less, more preferably 30 to 90. More preferably, it is 35-85. When the A hardness is too high, flexibility and elasticity are hardly exhibited, and when an adhesive body of different materials is produced, it tends to be difficult to absorb an impact applied to the joint surface.

  The melt flow rate (MFR) of the thermoplastic polymer composition measured by a method according to JIS K 7210 at 230 ° C. and a load of 2.16 kg (21.18 N) is preferably 1 to It is in the range of 50 g / 10 min, more preferably 1-40 g / 10 min, and still more preferably 2-30 g / min. When the MFR is within this range, good moldability can be obtained and the film can be easily produced.

  The adhesive strength of the thermoplastic polymer composition is preferably 20 N / 25 mm or more, more preferably 30 N / 25 mm or more, and further preferably 60 N / 25 mm or more in the compression molding method. The adhesive strength of 20 N / 25 mm or more is comparable to the adhesive strength in the case of performing a surface treatment such as a primer, and is an adhesive strength that can withstand practical use. Here, the adhesive strength is a value measured according to JIS K 6854-2 by the method described in Examples.

(Insert material)
There is no limitation in particular in the shape of the insert member used for this invention. The insert member used in the present invention is preferably at least one selected from the group consisting of ceramics, metals, and synthetic resins (thermoplastic resins and thermosetting resins).

  The ceramic that can be used for the insert member means a non-metallic inorganic material, and examples thereof include metal oxides, metal carbides, and metal nitrides. Examples include glass, cements, alumina, zirconia, zinc oxide ceramics, barium titanate, lead zirconate titanate, silicon carbide, silicon nitride, ferrites, and the like is preferable.

Examples of the metal that can be used for the insert member include iron, copper, aluminum, magnesium, nickel, chromium, zinc, and alloys containing them as components. Further, it may be a molded product having a metal surface formed by plating such as copper plating, nickel plating, chrome plating, tin plating, zinc plating, platinum plating, gold plating, or silver plating.
Moreover, light metals, such as aluminum and a magnesium alloy, are used for housing materials, such as an electronic / electric equipment, OA equipment, household appliances, and a member for motor vehicles, and such a housing material can also be used.

  Synthetic resins that can be used for the insert member include, for example, polyamide resin, polyester resin, polycarbonate resin, polyphenylene sulfide resin, (meth) acrylonitrile-butadiene-styrene resin, (meth) acrylonitrile-styrene resin, (meth) acrylic ester. -Butadiene-styrene resin, (meth) acrylic ester-styrene resin, butadiene-styrene resin, acrylic resin, epoxy resin, phenol resin, diallyl phthalate resin, polyimide resin, melamine resin, polyacetal resin, polysulfone resin, polyethersulfone resin , Polyetherimide resin, polyphenylene ether resin, polyarylate resin, polyetheretherketone resin, polystyrene resin, syndiotactic polystyrene Down resins, and polyolefin resins. These resin may be used individually by 1 type, and may be used in combination of 2 or more type.

The synthetic resin may contain an inorganic filler. Examples of the inorganic filler include calcium carbonate, talc, magnesium hydroxide, aluminum hydroxide, mica, clay, natural silicic acid, synthetic silicic acid, titanium oxide, carbon black, barium sulfate, glass fiber, and glass balloon. It is done. An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type. Among these, glass fiber is preferable.
The blending amount of the inorganic filler is preferably within a range in which the molding processability and mechanical strength of the synthetic resin containing the inorganic filler are not impaired, and is generally preferably 0.1% relative to 100 parts by mass of the synthetic resin. 1-100 mass parts, More preferably, it is 1-50 mass parts, More preferably, it is 3-40 mass parts.

(Resin member)
The resin member is not particularly limited as long as the adhesive film for insert molding adheres thereto, and may be composed of any of a thermoplastic resin and a thermosetting resin. When two or more resin members are bonded to one insert member, resin members made of resins having the same composition may be bonded, or resin members made of resins having different compositions or resins having different properties are bonded. You may let them. For example, at least one of a resin member made of a thermoplastic resin and a resin member made of a thermosetting resin can be bonded.
Examples of the thermoplastic resin forming the resin member include a styrene resin, a polycarbonate resin, a polyester resin, an acrylic resin, a polyolefin resin, and a polyamide resin.

  Examples of the styrene resin include polystyrene, high impact polystyrene, acrylonitrile-styrene resin, acrylonitrile-ethylene-styrene resin, acrylonitrile-butadiene-styrene resin, methyl methacrylate / butadiene / styrene copolymer), acrylonitrile / styrene / acrylic rubber. A copolymer etc. are mentioned.

Examples of the polycarbonate resin include aromatic polycarbonate, aliphatic polycarbonate, aromatic-aliphatic polycarbonate, and the like.
Examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyglycolic acid, and polylactic acid.
Examples of acrylic resins include poly (meth) methyl acrylate, poly (meth) ethyl acrylate, poly (meth) butyl acrylate, (meth) methyl acrylate- (meth) butyl acrylate copolymer, (meth ) Ethyl acrylate- (meth) butyl acrylate copolymer, (meth) methyl acrylate-styrene copolymer, and the like.
Examples of the polyolefin resin include polyethylene, polypropylene, poly-1-butene, polyisobutylene, random copolymer or block copolymer in any ratio of propylene and ethylene and / or 1-butene, and ethylene and propylene. Cyclic polyolefins such as ethylene-propylene-diene terpolymers having a diene component of 50% by weight or less in any proportion, polymethylpentene, a copolymer of cyclopentadiene and ethylene and / or propylene, ethylene or propylene and 50 Examples thereof include random copolymers and block copolymers with vinyl compounds of not more than% by weight.
Examples of polyamide resins include polycaproamide (nylon-6), polyhexamethylene adipamide (nylon-66), polytetramethylene adipamide (nylon-46), and polydodecanamide (nylon-12). .

  These resins may be used alone or as a polymer alloy in which two or more are arbitrarily combined. Furthermore, fillers such as talc, kaolin, mica, montmorillonite, glass fiber, and carbon fiber may be contained.

  Examples of the thermosetting resin that forms the resin member include epoxy resins, phenol resins, urethane resins, and unsaturated polyester resins.

[Film made of thermoplastic polymer composition]
In the method for producing an adhesive body of the present invention, a film made of the thermoplastic polymer composition is bonded to an insert member, and then a resin member is insert-molded on the film.
As a method for forming a film made of the thermoplastic polymer composition, various methods generally used for thermoplastic polymer compositions can be used. Specifically, any molding method such as an injection molding method, an extrusion molding method, a compression molding method, a blow molding method, a calendar molding method, a casting molding method, an inflation method, a belt method, or the like can be adopted. In particular, an extrusion method using a T die is preferable.

  The thickness of the film is usually 10 μm to 2.0 mm. Preferably they are 40 micrometers-1.5 mm, More preferably, they are 100 micrometers-1.0 mm, More preferably, they are 150 micrometers-500 micrometers. If the thickness of the film is 10 μm or more, the production of the film becomes easy, and it is possible to absorb the impact applied to the joint portion of the dissimilar material adhesive and the strain due to the difference in linear expansion coefficient. If the thickness of the film is 2.0 mm or less, it is easy to bond with the insert part, and the space required for the joint portion of the dissimilar material adhesive can be saved.

The film preferably has little tack (stickiness). When the tack is small, handling such as rewinding of the film becomes easy. Specifically, two films cut to a width of 25 mm are overlapped, and a 2 kg roll is applied twice at a speed of 10 mm / min and pressed. The peeling force when the T-type peeling is performed on the pressure-bonded film at a speed of 50 mm / min is preferably 1 N / 25 mm or less, more preferably 200 mN / 25 mm or less, and further preferably 50 mN / 25 mm or less. Preferably, it is most preferably 0 N / 25 mm.

The method for laminating a film made of a thermoplastic polymer composition (hereinafter sometimes simply referred to as “film”) to the insert member is not particularly limited, and any method may be employed, a lamination method. , Compression molding method, vacuum molding method, extrusion lamination method, two-color molding method, insert molding method, melt casting method, melt coating method, solution coating method and the like. In that case, you may heat either the film surface or the surface of an insert member, or both as needed. Although heating temperature changes with materials of an insert member, 120-240 degreeC is preferable and the heating temperature at the time of bonding the film which consists of a thermoplastic polymer composition to an insert member is more preferable, 120-190 degreeC, 130-170 degreeC Is more preferable. If the heating temperature is 120 ° C. or higher, good adhesion can be obtained, and if it is 240 ° C. or lower, damage to the insert member can be avoided.
For example, when a film is bonded to an insert member by a compression molding method, a film formed in advance is preliminarily formed into a predetermined shape and size, and is heated and compressed using a compression molding machine or the like. The film can be bonded to the insert member by applying pressure. At this time, on the surface that does not adhere to the adherend, a layer of nonpolar resin such as olefin resin, cyclic olefin resin or polytetrafluoroethylene resin is provided on the outermost layer as necessary for protection or decoration. It may be provided.
When the film is bonded to the insert member by the extrusion lamination method, the film is extruded onto the surface of the adherend made of ceramics, metal or synthetic resin, or its edge, which has been formed in a predetermined shape and size in advance. It is also possible to directly extrude a molten thermoplastic polymer composition extruded from a die having a predetermined shape attached to a machine and bond the film to an insert member.
When the insert member is a thermoplastic resin, the film can be bonded to the insert member by simultaneously extruding the molten thermoplastic resin composition and the thermoplastic resin from a die having a predetermined shape.
In order to bond the film to the insert member by insert molding, the film can be bonded to the insert member by setting the insert member in a mold and injection-molding the thermoplastic resin composition into a film thereon. .

[Method of manufacturing an adhesive body by insert molding]
In the method for producing an adhesive body of the present invention, a film made of the above thermoplastic polymer composition is bonded to an insert member by the method described above, the insert member is inserted into a mold having a predetermined shape, and a resin is then added. An adhesive body is obtained by filling. By filling the mold with resin, a resin member is formed on the film. By the method, an adhesive body in which the insert member and the resin member are integrated through a film made of the thermoplastic polymer composition can be obtained.

  There is no restriction | limiting in particular in the method of hold | maintaining an insert member in a metal mold | die, A well-known method can be employ | adopted, For example, the method of fixing using a pin etc. and the method of fixing with a vacuum line are mentioned. There is no restriction | limiting in particular in the molding method of a resin member, The general molding conditions of each resin can be diverted as it is.

An example of the manufacturing method in the present invention will be described below.
By holding the insert member 13 in which the film 12 made of the thermoplastic polymer composition is bonded to the mold 1 shown in FIGS. 1 and 2, and degassing from the suction circuit 11 (suction air flow path), The insert member 13 is brought into close contact with the mold cavity forming surface.
Next, after the mold 1 and the mold 2 are brought into contact with each other at the parting line L and clamped, they pass through the sprues 3, 3 A and 3 B and melt from the resin injection ports 6, 6 A and 6 B at the leading ends. After the resin is injected into the cavities 10, 10 </ b> A, and 10 </ b> B and the molten resin is cooled and solidified, the mold 1 and the mold 2 are opened, and a molded product in which the insert member and the resin member are integrally formed is taken out. . As described above, an adhesive body can be manufactured.

In the method of the present invention, since the film made of the thermoplastic polymer composition has less tack (stickiness), the handleability is good and the production efficiency is excellent.
The film can be bonded (adhered) to the insert member only by heating without applying a primer treatment or the like, has excellent flexibility, and can reduce the difference in linear expansion coefficient between members. Furthermore, since the film has excellent adhesiveness regardless of the polarity of the resin member to be bonded by insert molding, two or more resin members having different characteristics can be formed on one insert member with high adhesive strength. It is also possible, and the degree of freedom in designing the adhesive is improved. Moreover, it has the characteristic that a resin member can be adhere | attached on a film at the temperature of resin to insert. The adhesive obtained by the production method of the present invention has practically sufficient adhesiveness even when placed in an environment of 60 ° C. or higher, and can be used for a wide range of applications. An adhesive body obtained by the production method of the present invention is also included in the scope of the present invention.

  Adhesives obtained by the production method of the present invention include automobiles, motorcycles, ships, railway vehicles, aircraft and other members, indoor doors, partitions, furniture, system kitchens, housing materials such as bathtubs, electronic and electrical equipment, OA equipment, Although it can use suitably for household appliances, a building material, a container, office supplies, sports goods, a toy, etc., it is not limited to these.

EXAMPLES Hereinafter, although an Example etc. demonstrate this invention further in detail, this invention is not limited to these Examples at all.
In addition, each component used in the following Examples and Comparative Examples is as follows.

[Thermoplastic elastomer (A1)]
Nitrogen-substituted and dried pressure vessel was charged with 80 L of cyclohexane as a solvent and 0.047 L of sec-butyllithium (10 mass% cyclohexane solution) as an initiator. After the temperature was raised to 50 ° C., 2.3 L of styrene was added and polymerized for 3 hours. Subsequently, a mixture of 8.1 L of isoprene and 6.6 L of butadiene was added for polymerization for 4 hours, and 2.3 L of styrene was further added. For 3 hours. The obtained reaction liquid was poured into 80 L of methanol, and the precipitated solid was separated by filtration and dried at 50 ° C. for 20 hours to obtain a triblock copolymer composed of polystyrene block-poly (isoprene / butadiene) block-polystyrene block. It was.
Subsequently, 20 kg of a triblock copolymer composed of polystyrene block-poly (isoprene / butadiene) block-polystyrene block was dissolved in 200 L of cyclohexane, and palladium carbon (palladium supported amount: 5 mass%) was used as a hydrogenation catalyst. 5 mass% was added with respect to coalescence, and reaction was performed on the conditions of hydrogen pressure 2MPa and 150 degreeC for 10 hours. After cooling and releasing the pressure, palladium carbon is removed by filtration, the filtrate is concentrated, and further dried under vacuum to hydrogenate a triblock copolymer composed of polystyrene block-poly (isoprene / butadiene) block-polystyrene block. A product (hereinafter referred to as a thermoplastic elastomer (A1)) was obtained. The resulting thermoplastic elastomer (A1) has a weight average molecular weight of 380,000, a styrene content of 30% by mass, a hydrogenation rate of 97%, a molecular weight distribution of 1.04, and is contained in a poly (isoprene / butadiene) block 1 , 2-bond and 3,4-bond amount were 5 mol%.

[Thermoplastic elastomer (A2)]
A pressure-resistant container purged with nitrogen and dried is charged with 80 L of cyclohexane as a solvent and 0.34 L of sec-butyllithium (10 mass% cyclohexane solution) as an initiator, heated to 50 ° C., and then added with 4.0 L of styrene. The mixture was polymerized for 3 hours, followed by addition of a mixed solution of 14.2 L of isoprene and 11.6 L of butadiene for 4 hours of polymerization, and 4.0 L of styrene was further added for 3 hours of polymerization. The obtained reaction liquid was poured into 80 L of methanol, and the precipitated solid was separated by filtration and dried at 50 ° C. for 20 hours to obtain a triblock copolymer composed of polystyrene block-poly (isoprene / butadiene) block-polystyrene block. It was.
Subsequently, 20 kg of a triblock copolymer composed of polystyrene block-poly (isoprene / butadiene) block-polystyrene block was dissolved in 200 L of cyclohexane, and palladium carbon (palladium supported amount: 5 mass%) was used as a hydrogenation catalyst. 5 mass% was added with respect to coalescence, and reaction was performed on the conditions of hydrogen pressure 2MPa and 150 degreeC for 10 hours. After cooling and releasing the pressure, the palladium carbon is removed by filtration, the filtrate is concentrated, and further dried under vacuum to hydrogenate a triblock copolymer composed of polystyrene block-poly (isoprene / butadiene) block-polystyrene block. A product (hereinafter referred to as a thermoplastic elastomer (A2)) was obtained. The resulting thermoplastic elastomer (A2) has a weight average molecular weight of 100,000, a styrene content of 30% by mass, a hydrogenation rate of 97%, a molecular weight distribution of 1.02, 1,2-bonds and 3,4-bonds. The total amount was 5 mol%.

[Thermoplastic elastomer (A3)]
Nitrogen-substituted and dried pressure vessel was charged with 80 L of cyclohexane and 0.26 L of sec-butyllithium (10% by mass cyclohexane solution) as an initiator, heated to 50 ° C., and then added with 7.5 L of styrene. Then, 10.7 L of isoprene was added for 4 hours to perform polymerization, and 7.5 L of styrene was further added for 3 hours to perform polymerization. The obtained reaction solution was poured into 80 L of methanol, and the precipitated solid was separated by filtration and dried at 50 ° C. for 20 hours to obtain a triblock copolymer composed of polystyrene block-polyisoprene block-polystyrene block.
Subsequently, 20 kg of a triblock copolymer composed of polystyrene block-polyisoprene block-polystyrene block was dissolved in 200 L of cyclohexane, and palladium carbon (palladium supported amount: 5% by mass) was added to the copolymer as a hydrogenation catalyst. 5 mass% was added, and the reaction was performed for 10 hours under the conditions of a hydrogen pressure of 2 MPa and 150 ° C. After cooling and releasing the pressure, the palladium carbon was removed by filtration, the filtrate was concentrated, and further dried under vacuum to obtain a hydrogenated product of a triblock copolymer consisting of polystyrene block-polyisoprene block-polystyrene block (hereinafter, A thermoplastic elastomer (referred to as A3) was obtained. The resulting thermoplastic elastomer (A3) has a weight average molecular weight of 80,000, a styrene content of 65% by mass, a hydrogenation rate of 95%, a molecular weight distribution of 1.02, 1,2-bonds and 3,4-bonds. The total amount was 7 mol%.

[Thermoplastic elastomer (A4)]
A pressure-resistant container purged with nitrogen and dried was charged with 64 L of cyclohexane as a solvent and 0.20 L of sec-butyllithium (10% by mass cyclohexane solution) as an initiator, and 0.3 L of tetrahydrofuran as an organic Lewis base (lithium in the initiator) (Equivalent to 15 times the stoichiometric ratio to atoms). After the temperature was raised to 50 ° C., 2.3 L of styrene was added for polymerization for 3 hours, then 23 L of isoprene was added for polymerization for 4 hours, and 2.3 L of styrene was further added for polymerization for 3 hours. The obtained reaction solution was poured into 80 L of methanol, and the precipitated solid was separated by filtration and dried at 50 ° C. for 20 hours to obtain a triblock copolymer composed of polystyrene-polyisoprene-polystyrene.
Subsequently, 10 kg of a triblock copolymer composed of polystyrene-polyisoprene-polystyrene was dissolved in 200 L of cyclohexane, and palladium carbon (palladium supported amount: 5% by mass) as a hydrogenation catalyst was 5% by mass with respect to the copolymer. The reaction was carried out for 10 hours under the conditions of hydrogen pressure of 2 MPa and 150 ° C. After allowing to cool and release, palladium carbon is removed by filtration, the filtrate is concentrated, and further dried under vacuum to give a hydrogenated product of a triblock copolymer consisting of polystyrene-polyisoprene-polystyrene (hereinafter, thermoplastic elastomer). (Referred to as (A4)). The resulting thermoplastic elastomer (A4) has a weight average molecular weight of 107,000, a styrene content of 21% by mass, a hydrogenation rate of 85%, a molecular weight distribution of 1.04, and 1,2-contained in the polyisoprene block. The total amount of bonds and 3,4-bonds was 60 mol%.

[Thermoplastic elastomer (A5)]
A pressure-resistant container purged with nitrogen and dried was charged with 150 L of cyclohexane as a solvent, 0.22 L of sec-butyllithium (10% by mass cyclohexane solution) as an initiator, and 0.3 L of tetrahydrofuran as a Lewis base (lithium atoms in the initiator). In contrast, the stoichiometric ratio was 14 times equivalent). After raising the temperature to 50 ° C., 0.72 L of styrene is added and polymerized for 3 hours. Subsequently, a mixed solution of 12.6 L of isoprene and 14.0 L of butadiene is added for polymerization for 4 hours, and 2.2 L of styrene is further added. For 3 hours. The obtained reaction liquid was poured into 80 L of methanol, and the precipitated solid was separated by filtration and dried at 50 ° C. for 20 hours to obtain a triblock copolymer composed of polystyrene-poly (isoprene / butadiene) -polystyrene.
Subsequently, 10 kg of a triblock copolymer composed of polystyrene-poly (isoprene / butadiene) -polystyrene is dissolved in 200 L of cyclohexane, and palladium carbon (palladium supported amount: 5% by mass) is added to the copolymer as a hydrogenation catalyst. The reaction was carried out for 10 hours under the conditions of a hydrogen pressure of 2 MPa and 150 ° C. After allowing to cool and release the pressure, the palladium carbon is removed by filtration, the filtrate is concentrated, and further dried under vacuum to give a hydrogenated product of a triblock copolymer composed of polystyrene-poly (isoprene / butadiene) -polystyrene (hereinafter referred to as “polystyrene”). A thermoplastic elastomer (referred to as A5) was obtained. The resulting thermoplastic elastomer (A5) has a weight average molecular weight of 165,000, a styrene content of 13% by mass, a hydrogenation rate of 85%, a molecular weight distribution of 1.02, 1,2-bond amount and 3,4. -The total amount of bonds was 63 mol%.

[Thermoplastic elastomer (A6)]
A pressure-resistant vessel purged with nitrogen and dried was charged with 120 L of cyclohexane as a solvent, 0.12 L of sec-butyllithium (10 mass% cyclohexane solution) as an initiator, and 0.3 L of tetrahydrofuran as a Lewis base (lithium atoms in the initiator) The stoichiometric ratio is equivalent to 26 times). After the temperature was raised to 50 ° C., 3.6 L of styrene was added for polymerization for 3 hours, then 20.0 L of isoprene was added for polymerization for 4 hours, and further 3.6 L of styrene was added for polymerization for 3 hours. The obtained reaction solution was poured into 80 L of methanol, and the precipitated solid was separated by filtration and dried at 50 ° C. for 20 hours to obtain a triblock copolymer composed of polystyrene-polyisoprene-polystyrene.
Subsequently, 10 kg of a triblock copolymer composed of polystyrene-polyisoprene-polystyrene was dissolved in 200 L of cyclohexane, and palladium carbon (palladium supported amount: 5% by mass) as a hydrogenation catalyst was 5% by mass with respect to the copolymer. The reaction was carried out for 10 hours under the conditions of hydrogen pressure of 2 MPa and 150 ° C. After allowing to cool and release, palladium carbon is removed by filtration, the filtrate is concentrated, and further dried under vacuum to give a hydrogenated product of a triblock copolymer consisting of polystyrene-polyisoprene-polystyrene (hereinafter, thermoplastic elastomer). (Referred to as (A6)). The resulting thermoplastic elastomer (A6) has a weight average molecular weight of 320,000, a styrene content of 33% by mass, a hydrogenation rate of 90%, a molecular weight distribution of 1.07, a 1,2-bond amount and 3,4. -The total amount of bonds was 54 mol%.

[Thermoplastic elastomer (A7)]
A pressure-resistant container purged with nitrogen and dried was charged with 86 L of cyclohexane as a solvent and 0.22 L of sec-butyllithium (10 mass% cyclohexane solution) as an initiator, and 0.02 L of ethylene glycol dimethyl ether as an organic Lewis base (in the initiator) The stoichiometric ratio was 0.7 times as large as that of lithium atoms. After the temperature was raised to 50 ° C., 2.3 L of styrene was added for polymerization for 3 hours, subsequently, 25.5 L of butadiene was added for polymerization for 4 hours, and 2.3 L of styrene was further added for polymerization for 3 hours. The obtained reaction solution was poured into 80 L of methanol, and the precipitated solid was separated by filtration and dried at 50 ° C. for 20 hours to obtain a triblock copolymer composed of polystyrene-polybutadiene-polystyrene.
Subsequently, 10 kg of a triblock copolymer composed of polystyrene-polybutadiene-polystyrene is dissolved in 200 L of cyclohexane, and 5% by mass of palladium carbon (palladium supported amount: 5% by mass) is added to the copolymer as a hydrogenation catalyst. Then, the reaction was carried out for 10 hours under conditions of a hydrogen pressure of 2 MPa and 150 ° C. After allowing to cool and release the pressure, palladium carbon is removed by filtration, the filtrate is concentrated, and further dried under vacuum to give a hydrogenated product of a triblock copolymer composed of polystyrene-polybutadiene-polystyrene (hereinafter, thermoplastic elastomer ( A7)) was obtained. The resulting thermoplastic elastomer (A7) has a weight average molecular weight of 126,000, a styrene content of 21% by mass, a hydrogenation rate of 95%, a molecular weight distribution of 1.11 and 1,2-bonds contained in the polybutadiene block. The amount was 78 mol%.

[Thermoplastic elastomer (A8)]
A pressure-resistant container purged with nitrogen and dried was charged with 80 L of cyclohexane as a solvent, 0.40 L of sec-butyllithium (10% by mass cyclohexane solution) as an initiator, and 0.6 L of tetrahydrofuran as an organic Lewis base (lithium in the initiator). (Equivalent to 15 times the stoichiometric ratio to atoms). After raising the temperature to 50 ° C., 4.2 L of styrene was added for polymerization for 3 hours, 28 L of isoprene was subsequently added for polymerization for 4 hours, and 4.2 L of styrene was further added for 3 hours of polymerization. The obtained reaction solution was poured into 80 L of methanol, and the precipitated solid was separated by filtration and dried at 50 ° C. for 20 hours to obtain a triblock copolymer composed of polystyrene-polyisoprene-polystyrene.
Subsequently, 20 kg of a triblock copolymer composed of polystyrene-polyisoprene-polystyrene was dissolved in 200 L of cyclohexane, and palladium carbon (palladium supported amount: 5% by mass) as a hydrogenation catalyst was 5% by mass with respect to the copolymer. The reaction was carried out for 10 hours under the conditions of hydrogen pressure of 2 MPa and 150 ° C. After allowing to cool and release, palladium carbon is removed by filtration, the filtrate is concentrated, and further dried under vacuum to give a hydrogenated product of a triblock copolymer consisting of polystyrene-polyisoprene-polystyrene (hereinafter, thermoplastic elastomer). (Referred to as (A8)). The resulting thermoplastic elastomer (A8) has a weight average molecular weight of 72,800, a styrene content of 30% by mass, a hydrogenation rate of 90%, a molecular weight distribution of 1.04, and 1,2-contained in the polyisoprene block. The total amount of bonds and 3,4-bonds was 60 mol%.

[Polyvinyl acetal resin (B1-1)]
To an aqueous solution in which 100 g of a polyvinyl alcohol resin having an average polymerization degree of 500 and a saponification degree of 99 mol% was dissolved, 75 g of n-butyraldehyde and 110 g of 35 to 37% hydrochloric acid were added and agitated to precipitate the resin. Wash until pH = 6 according to a known method, suspend in sodium hydroxide aqueous solution, perform after-treatment with stirring, wash until pH = 7, until volatile content is 0.3% By drying, a polyvinyl acetal resin (B1-1) having an acetalization degree of 80 mol% was obtained.

[Polyvinyl acetal resin (B1-2)]
79 g of n-butyraldehyde and 130 g of 35-37% hydrochloric acid were added to an aqueous solution in which 100 g of polyvinyl alcohol resin having an average polymerization degree of 1000 and a saponification degree of 99 mol% was dissolved, and agitated by stirring to precipitate a resin. Wash until pH = 6 according to a known method, suspend in sodium hydroxide aqueous solution, perform after-treatment with stirring, wash until pH = 7, until volatile content is 0.3% By drying, a polyvinyl acetal resin (B1-2) having an acetalization degree of 80 mol% was obtained.

[Polar group-containing polypropylene resin (B2-1)]
42 g of polypropylene “Prime Polypro F327” (manufactured by Prime Polymer Co., Ltd.), 160 mg of maleic anhydride and 42 mg of 2,5-dimethyl-2,5-di (tertiary butyl peroxy) hexane, 180 ° C. and screw using a batch mixer Melt kneading was performed at a rotation speed of 40 rpm. MFR [230 ° C., load 2.16 kg (21.18 N)] of the obtained kneaded product (polar group-containing polypropylene resin (B2-1)) was 6 g / 10 min, and the maleic anhydride concentration was 0.3%. There was a melting point of 138 ° C.
The maleic anhydride concentration is a value obtained by titrating the obtained kneaded product with a methanol solution of potassium hydroxide, and the same applies hereinafter. The melting point is a value read from the endothermic peak of the differential scanning calorimetry curve when the temperature is raised at 10 ° C./min, and so on.

[Polar group-containing polypropylene resin (B2-2)]
42 g of polypropylene “Novatech PP FG3DE (manufactured by Nippon Polypro)”, 160 mg of maleic anhydride and 42 mg of 2,5-dimethyl-2,5-di (tertiarybutylperoxy) hexane, 180 ° C. and screw using a batch mixer Melt kneading was performed at a rotation speed of 40 rpm. The obtained kneaded product (polar group-containing polypropylene resin (B2-2)) had an MFR [230 ° C., load 2.16 kg (21.18 N)] of 10 g / 10 min and a maleic anhydride concentration of 0.3%. There was a melting point of 143 ° C.

[Polar group-containing polypropylene resin (B2-3)]
42 g of polypropylene “Novatech PP F113G (manufactured by Prime Polymer)”, 5 g of maleic anhydride and 1.3 g of 2,5-dimethyl-2,5-di (tertiarybutylperoxy) hexane were mixed at 200 ° C. using a batch mixer. And it knead | mixed and kneaded on the conditions of screw rotation speed 100rpm. MFR [230 ° C., load 2.16 kg (21.18 N)] of the obtained kneaded product (polar group-containing polypropylene resin (B2-3)) was 250 g / 10 minutes, and the maleic anhydride concentration was 3.0%. There was a melting point of 161 ° C.

[Polar group-containing polypropylene resin (B2-4)]
42 g of polypropylene “Novatech PP E111G (manufactured by Prime Polymer)”, 8.4 g of maleic anhydride and 126 mg of 2,5-dimethyl-2,5-di (tertiarybutylperoxy) hexane were mixed at 200 ° C. using a batch mixer. And it knead | mixed and kneaded on the conditions of screw rotation speed 100rpm. MFR [230 ° C., load 2.16 kg (21.18 N)] of the obtained kneaded product (polar group-containing polypropylene resin (B2-4)) was 80 g / 10 minutes, and the maleic anhydride concentration was 6.0%. The melting point was 135 ° C.

[Polar group-containing polyethylene resin (B2′-5)]
42 g of polyethylene “Neozex 0434N” (manufactured by Prime Polymer Co., Ltd.), 160 mg of maleic anhydride and 42 mg of 5-dimethyl-2,5-di (tertiarybutylperoxy) hexane, 180 ° C. and screw rotation speed of 40 rpm using a batch mixer The mixture was melt kneaded under the following conditions. MFR [190 ° C., load 2.16 kg (21.18 N)] of the obtained kneaded product (polar group-containing polyethylene resin (B2′-5)) was 2 g / 10 minutes, and the maleic anhydride concentration was 0.3%. The melting point was 117 ° C.

[Polar group-containing olefin copolymer (C1-1)]
Ethylene-methyl acrylate copolymer “Elvalloy (registered trademark) AC 1820AC” (methyl acrylate content: 20% by mass, MFR [190 ° C., load 2.16 kg (21.18 N)]: 8 g / 10 min, Mitsui・ DuPont Polychemical Co., Ltd.)

[Polar group-containing olefin copolymer (C1-2)]
Ethylene-methyl acrylate copolymer “Elvalloy (registered trademark) AC 1609AC” (methyl acrylate content: 9% by mass, MFR [190 ° C., load 2.16 kg (21.18 N)]: 6 g / 10 min, Mitsui・ DuPont Polychemical Co., Ltd.)

[Polar group-containing olefin copolymer (C1-3)]
Ethylene-ethyl acrylate copolymer “ethylene-ethyl acrylate copolymer NUC-6170” (ethyl acrylate content: 18% by mass, MFR [190 ° C., load 2.16 kg (21.18 N)]: 6 g / 10 min., Made by Nihon Unicar)

[Thermoplastic elastomer having a polar group (C2-1)]
Charge 0.51 L of sec-butyllithium (10% by mass cyclohexane solution) as an initiator, and sequentially add 3.5 L of styrene, 13.1 L of isoprene and 11.8 L of butadiene, and 3.5 L of styrene as monomers to be polymerized. Polymerization reaction and hydrogenation reaction are performed in the same manner as the thermoplastic elastomer (A1) except that 0.05 L of ethylene oxide is added, and polystyrene-poly (isoprene / butadiene having a hydroxyl group at the end of the molecular main chain. ) -Polystyrene triblock copolymer hydrogenated product 20 kg (hereinafter referred to as terminal-modified hydrogenated block copolymer (x1)) was obtained. The terminal-modified hydrogenated block copolymer (x1) had a styrene content of 30% by mass, a hydrogenation rate of 95%, a weight average molecular weight of 200,000, and an average hydroxyl value of 0.9. Next, 100 parts by mass of the terminal-modified hydrogenated block copolymer (x1) obtained and 100 parts by mass of thermoplastic polyurethane (“Kuramylon U 2000” manufactured by Kuraray Co., Ltd .: polyester-based polyurethane elastomer having aliphatic polyester as a soft segment) The parts were dry blended and melt kneaded using a twin screw extruder under conditions of a cylinder temperature of 220 ° C. and a screw rotation speed of 150 rpm, and then extruded and cut to produce pellets. Unreacted polyurethane was extracted and removed from the obtained pellets using dimethylformamide, and then unreacted terminal-modified hydrogenated block copolymer (x1) was extracted and removed using cyclohexane. The residual solid content was dried to obtain a thermoplastic elastomer (C2-1) having a melt viscosity of 10 kPa · s in which the terminal-modified hydrogenated block copolymer (x1) and the thermoplastic polyurethane block were bonded.

[Tackifying resin (D1)]
Hydrogenated aromatic hydrocarbon resin “Regalite 1100” (manufactured by Eastman Chemical), softening point 100 ° C.
[Tackifying resin (D2)]
Hydrogenated aromatic hydrocarbon resin “Regalite 1125” (manufactured by Eastman Chemical), softening point 123 ° C.
[Tackifying resin (D3)]
Hydrogenated terpene resin “Clearon M115” (manufactured by Yasuhara Chemical), softening point 115 ° C.
[Tackifying resin (D4)]
Hydrogenated terpene resin “Clearon P150” (manufactured by Yasuhara Chemical), softening point 152 ° C.
[Softener (E1)]
Paraffin process oil “Diana Process PW-90” (made by Idemitsu Kosan Co., Ltd.)

Production of test pieces and measurement or evaluation of physical properties in Examples and Comparative Examples were performed as follows, and the results were summarized in a table.
(1) Measurement of melt flow rate (MFR) About the thermoplastic polymer composition produced by the following Examples and Comparative Examples, the method according to JIS K 7210 was performed at 230 ° C. and the load was 2.16 kg (21.18 N). The MFR was measured under the conditions described above and used as an index of molding processability. The larger the MFR value, the better the moldability.

(2) Measurement of hardness The thermoplastic polymer composition films prepared in the following examples and comparative examples were stacked to a thickness of 6 mm, and the A hardness was measured with a type A durometer according to JIS K 6253.

(3) Measurement of T-type peeling force A film made of a thermoplastic polymer composition produced by the following examples and comparative examples was cut into a 25 mm width, and two sheets were overlapped, and 2 kg rolls were rolled at a speed of 10 mm / min. It was made to crimp over. The peel force when the T-type peel was performed on the pressure-bonded film at a speed of 50 mm / min was measured. The T-type peel force is an index of film tack.

(4) Measurement of adhesive strength For the laminate (adhesive body) of PET / thermoplastic polymer composition / aluminum plate produced by the following method, the peel strength between the layer made of the thermoplastic polymer composition and the aluminum plate was measured according to JIS. In accordance with K 6854-2, the adhesive strength was measured under the conditions of a peeling angle of 180 °, a tensile speed of 50 mm / min, and an environmental temperature of 23 ° C. or 60 ° C. The adhesive strength at 60 ° C. is an index of heat resistance. The temperature described in the aluminum adhesive strength in Tables 2 to 5 is (molding temperature (° C.) − Peeling temperature (° C.)).

<Production of laminate with aluminum plate>
The pellets of the thermoplastic polymer composition produced according to the following examples and comparative examples were compression molded for 3 minutes using a compression molding machine at 230 ° C. and a load of 100 kgf / cm ² (9.8 N / mm ² ). As a result, a sheet having a thickness of 1 mm of the thermoplastic polymer composition was obtained. The surfaces of both surfaces of an aluminum plate (insert member (a)) having a length of 75 mm, a width of 25 mm, and a thickness of 1 mm were washed using a surfactant aqueous solution and distilled water in this order as a washing liquid and dried. The aluminum plate, the thermoplastic polymer composition sheet, and a 50 μm thick polyethylene terephthalate (PET) sheet are stacked in this order, and the center of a metal spacer having an outer dimension of 200 mm × 200 mm, an inner dimension of 150 mm × 150 mm, and a thickness of 2 mm. Placed in the department.
The overlapped sheet and a metal spacer are sandwiched between polytetrafluoroethylene sheets and further sandwiched between metal plates from the outside. Using a compression molding machine, the load is 20 kgf / cm ² (2N under the temperature conditions shown in Tables 2 to 5. / Mm ² ) for 3 minutes to obtain a laminate composed of PET / thermoplastic polymer composition / aluminum plate.

[Examples 1-46, Comparative Examples 1-7]
After melt-kneading each component at a ratio shown in Tables 2 to 6 using a twin screw extruder at 230 ° C. and a screw rotation of 200 rpm, it is extruded into a strand shape, cut, and pellets of a thermoplastic polymer composition Got.
In Examples 1 to 42 and Comparative Examples 1 to 7, the obtained thermoplastic polymer compositions had MFR, hardness, T-type peeling force, and adhesive strength with an aluminum plate (aluminum adhesive strength: molding temperature ( ° C) -peeling temperature (° C) was measured according to the measurement method described above. The results are shown in Tables 2-5.

In all Examples and Comparative Examples, an adhesive body was produced by insert molding according to the following method, and the insert adhesiveness was evaluated.
<Evaluation method of insert adhesiveness>
About the thermoplastic polymer composition obtained by the Example and comparative example which were described in Table 2 and Table 6, the pellet was shape | molded 230 degreeC and 10 kgf for 3 minutes with the compression molding machine, and the film about 200 micrometers thick was obtained.
On the other hand, for the thermoplastic polymer compositions obtained in Examples and Comparative Examples described in Tables 3 to 5, the pellets were placed in a hopper of a single screw extruder in which the pellets were set to a cylinder and a die temperature of 190 ° C. and a screw rotation speed of 60 rpm. A film having a width of about 30 cm and a thickness of about 200 μm was obtained using a T-type die that was charged and attached to the tip of the die.
The obtained film and the following insert members described in Tables 2 to 6 were stacked, sandwiched from outside by a polytetrafluoroethylene sheet, further sandwiched from outside by a metal plate, and listed in Tables 2 and 6 using a compression molding machine. The film of the thermoplastic polymer composition was formed by compression molding at 200 ° C. for the examples and comparative examples and at 160 ° C. for each of the examples and comparative examples described in Tables 3 to 5 without increasing the pressure for 3 minutes. A bonded insert member was obtained.

Next, the insert member was inserted into a mold having a cavity of length 100 mm × width 35 mm × depth 2 mm and fixed with a vacuum line, and then filled with the following molding resin described in Tables 2 to 6 A member was formed to obtain an adhesive. The obtained bonded body was evaluated as “X” when the insert member and the resin member were easily peeled by hand, “Δ” when there was resistance when being peeled, and “◯” when it was not peeled off.
(Insert material)
In manufacturing the bonded body, the surface of both surfaces of each of the following insert members having a length of 100 mm, a width of 35 mm and a thickness of 1 mm was washed using an aqueous surfactant solution and distilled water in this order and dried at 65 ° C. Using.
Insert member (a): Aluminum plate (A5052P)
Insert member (b): Glass Insert member (c): Steel plate (SPCC)
Insert member (d): Galvanized steel sheet: (SECC)
Insert member (e): Stainless steel (SUS304)
Insert member (f): Copper plate (C1100P)
(Resin member)
PA6: Nylon 6 “UBE Nylon 6 1013B” manufactured by Ube Industries, Ltd. PBT: Polybutylene terephthalate “Toraycon 1401” manufactured by Toray Industries, Inc. PC: Polycarbonate “Panlite 1225”, manufactured by Teijin Chemicals Ltd. ABS / PC: Acrylonitrile butadiene styrene resin / polycarbonate alloy "Novaloy S1500" Teijin Chemicals PPE / PS: Polyphenylene ether / polystyrene alloy "Zylon 500H" Asahi Kasei PP: Polypropylene "Novatech PP MA3" Nippon Polypro PE: Polyethylene "Novatech PE UE320" Nippon Polyethylene

The thermoplastic polymer compositions used in Examples 1 to 42 show excellent adhesion to aluminum without performing primer treatment, and good adhesives between aluminum and various resins having different polarities. I was able to get it. Moreover, it is excellent in flexibility, and can absorb a strain caused by an impact applied to a joint portion or a difference in linear expansion coefficient. Moreover, since there is little tack, handling is also easy.
In Examples 4 to 7 using the compatibilizer C2-1, the adhesive strength with aluminum was further improved. In Examples 8 to 27, the moldability was improved, and film production by extrusion became possible. Even when the heating temperature at the time of bonding the film of the thermoplastic polymer composition and the insert member was 160 ° C., which is a relatively low temperature, a good bonded body could be obtained. Furthermore, moldability improved more by adding tackifying resin D1-D4.
In Examples 13 to 42 in which B2-1 to B2-4 are used as the adhesion imparting component, it can be seen that an adhesive body having high adhesive strength with aluminum and high heat resistance can be obtained even at 60 ° C.
Moreover, in Examples 43-46, the favorable adhesive body which consists of glass, various metals, and a polypropylene is obtained, The dissimilar adhesive body of various combinations can be manufactured with the manufacturing method of this invention. I understand that.

  On the other hand, in Comparative Examples 1, 2, 4 and 5 containing no or little adhesion-imparting component, the adhesiveness to aluminum was poor, and the insert member was easily detached from the adhesive. Moreover, in Comparative Examples 3 and 6 having too many adhesion imparting components, the flexibility of the film was insufficient, and in Comparative Example 3, the adhesiveness with the molding resin was also impaired, and a good bonded body could not be obtained. In Comparative Example 7 in which the polar group-containing polyethylene resin (B2′-5) was used as an adhesion-imparting component, the adhesion with aluminum was impaired, and a good bonded body could not be obtained.

  Since the manufacturing method of the adhesive body of this invention can insert-mold several types of resin on the same film, it is useful for manufacture of the adhesive body of a complicated structure. Furthermore, since an adhesive body in which the insert member and the resin member are bonded easily and firmly without using an adhesive can be obtained through the film, the adhesive body is suitable for applications requiring strength and durability. It is useful for the production of

Claims (7)

  Polyvinyl acetal with respect to 100 parts by mass of a block copolymer having a polymer block containing an aromatic vinyl compound unit and a polymer block containing a conjugated diene compound unit or a hydrogenated product of the thermoplastic elastomer (A) A block copolymer having 10 to 100 parts by mass of a resin (B1), a polymer block containing an aromatic vinyl compound unit, and a polymer block containing a conjugated diene compound unit, or a hydrogenated product thereof, which is polar The manufacturing method of the adhesive body which bonds the film which consists of a thermoplastic polymer composition containing the thermoplastic elastomer (C2) which has group to an insert member, and then insert-molds a resin member on this film. Polyvinyl acetal resin (B1) is polyvinyl butyral, the production method of the adhesive of claim 1.   A polar group with respect to 100 parts by mass of a block copolymer having a polymer block containing an aromatic vinyl compound unit and a polymer block containing a conjugated diene compound unit or a hydrogenated product of the thermoplastic elastomer (A) A block copolymer having 10 to 100 parts by mass of the polypropylene-containing resin (B2), a polymer block containing an aromatic vinyl compound unit, and a polymer block containing a conjugated diene compound unit, or a hydrogenated product thereof. Then, a film made of a thermoplastic polymer composition containing a compatibilizer (C) which is a thermoplastic elastomer (C2) having a polar group is bonded to an insert member, and then a resin member is insert-molded on the film The manufacturing method of an adhesive body. The thermoplastic elastomer (A) is a polymer block containing an aromatic vinyl compound unit, an isoprene unit, a butadiene unit or an isoprene in which the amount of 1,2-bond and 3,4-bond is 40 mol% or more in total. The manufacturing method of the adhesive body as described in any one of Claims 1-3 which is a block copolymer which has / polymer block containing a / butadiene unit, or its hydrogenated substance. The method for producing an adhesive body according to any one of claims 1 to 4 , wherein the film is a single layer film. The method for producing an adhesive body according to any one of claims 1 to 5 , wherein the insert member is at least one selected from the group consisting of ceramics, metals, thermoplastic resins, and thermosetting resins. The manufacturing method of the adhesive body as described in any one of Claims 1-6 which bonds the film which consists of a thermoplastic polymer composition to an insert member by heating, and this heating temperature is 120-240 degreeC.

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