JP7319901B2 - Adhesion improving agent, adhesive, and method for improving adhesion - Google Patents

Description

TECHNICAL FIELD The present invention relates to an adhesion improving agent comprising polysilane, an adhesive containing this adhesion improving agent, and a method for improving adhesion using polysilane.

In recent years, in various fields including the automobile industry, there has been a shift from metal materials to resin materials, or the use of a combination of metal and resin materials, in order to improve fuel efficiency and reduce weight. Materialization is in progress. Especially in the European automobile industry, fuel efficiency regulations are progressing, and it is expected that the use of multi-materials will accelerate further in the future. When using a combination of two or more types of materials in this manner, techniques for adhering and bonding these materials are essential. Conventionally, methods such as mechanical joining (or fastening) using screws, bolts, rivets, etc., and friction stir welding (friction stir welding or FSW) are often used for joining. However, the mechanical joining may increase the weight and cost due to bolts and the like, and stress concentration may occur at the joining portion, which may cause breakage. Friction stir welding is not only incapable of handling complex shapes, but also limits the types of materials that can be applied, so there is a risk of increasing restrictions in terms of product design.

On the other hand, a method of adhering two base materials (adherends or adherends) with an adhesive is also known. For example, Japanese Patent Application Laid-Open No. 2013-117011 (Patent Document 1) describes that two cold-rolled steel sheets are bonded using a predetermined two-component curing acrylic composition. However, as in Patent Document 1, although there are adhesives that can exhibit excellent adhesive strength between similar materials such as metal-to-metal, glass-to-glass, and resin-to-resin, high adhesive strength can be obtained between dissimilar materials. There is no adhesive that can adhere, and development is sought.

As an adhesive composition for bonding two dissimilar materials, Japanese Patent Application Laid-Open No. 55-84370 (Patent Document 2) describes a semi-inorganic compound that converts to a ceramic made of SiC, a ceramic powder and / or a metal powder. and a polysilane is described as the semi-inorganic compound.

In addition, JP 2013-189555 (Patent Document 3), JP 2018-123262 (Patent Document 4), and US Patent Application Publication No. 2018/0186133 (Patent Document 5) contain polysilane. Adhesives or adhesives are described.

Patent Document 3 discloses a thermosetting epoxy adhesive containing an epoxy compound and an aluminum chelate-silanol curing catalyst system, which adhesive contains a polysilane compound that provides a silanol group that acts on an aluminum chelating agent when irradiated with ultraviolet rays. is disclosed. It also describes that the polysilane compound is added to generate cationic species that initiate cationic polymerization of the epoxy compound.

Patent Document 4 discloses a pressure-sensitive adhesive composition containing a silane compound (A) containing a Si—Si bond, and further containing a (meth)acrylic compound (B), a cross-linking agent (C), and the like. It also describes that a polysilane compound as the silane compound (A) containing Si--Si bonds can improve the durability of the pressure-sensitive adhesive layer.

Patent Document 5 discloses an adhesive composition comprising an organosilicon polymer, a silicon coupling agent, a polyester having a carboxyl group and a solvent. Further, it is disclosed that the adhesive layer contains polysiloxane or polysilane as the organosilicon polymer, and that if the content of the organosilicon polymer is out of the predetermined range, the mechanical strength of the adhesive layer becomes insufficient.

JP 2013-117011 A JP-A-55-84370 JP 2013-189555 A JP 2018-123262 A U.S. Patent Application Publication No. 2018/0186133

In Patent Document 2, this composition needs to be heated at 400 to 2000° C. in a non-oxidizing atmosphere. Resin materials with low heat resistance cannot be easily adhered.

In particular, non-polar substrates such as resins with low surface energy (or surface free energy) such as polyethylene and polypropylene are difficult to bond even between materials of the same type. Since it is extremely difficult to bond them together and there is no useful adhesive, the above-mentioned bonding method using screws, rivets, or the like is unavoidably adopted in many cases.

In Patent Documents 3 and 4, although it is described that polysilane is used as a polymerization initiator that generates cationic species or as a component that improves durability against floating or foaming in a high temperature environment, adhesion Nothing is said about improving power.

In addition, in Patent Documents 3 and 4, since the adhesive or pressure-sensitive adhesive contains a curable resin having a three-dimensional network chemical structure, a curing agent (or a cross-linking agent), a curing catalyst, etc. are adjusted according to the type of resin. It is also necessary to mix an appropriate amount of the adhesive with heat or apply heat or light energy to harden it, and the work from preparation to adhesion tends to be complicated. Therefore, productivity cannot be improved as compared with adhesives using thermoplastic resins such as solvent-type and hot-melt-type adhesives. In addition, although Patent Document 4 is an adhesive, the adhesive is also called a pressure-sensitive adhesive, and is required to have properties such as reworkability that does not leave a trace even when peeled off. Often not expected.

Although polysilane is exemplified in Patent Document 5, silicone (“SEBA-350-6” manufactured by Green & UL Foam Technology Ltd.) is used in Examples, and substantially only polysiloxane is used as the organosilicon polymer. is described, and nothing is specifically disclosed about polysilane. Further, although it is described that the organosilicon polymer affects the mechanical strength, it is also described that the content of the silicon coupling agent and the polyester having a carboxyl group affects the adhesiveness.

Accordingly, an object of the present invention is to provide an adhesion improver capable of effectively improving the adhesion force even when bonding different materials, and an adhesive or adhesive composition (or resin composition) containing the adhesion improver. ), and to provide a method for improving adhesion.

Another object of the present invention is an adhesion improver capable of preparing an adhesive (or a substrate such as a resin substrate) that can be easily adhered with high adhesion without pretreatment, and this adhesion improver. and a method for improving adhesion.

The inventors of the present invention have made intensive studies to achieve the above object, and found that, although polysilane itself hardly exhibits adhesiveness, an adhesive agent containing polysilane, etc., is not capable of adhering dissimilar materials. The inventors have found that the adhesive force can be effectively improved even if there is a pretreatment, and that the adhesive force can be easily (efficiently or with high productivity) without pretreatment, and the present invention has been completed.

That is, the adhesion improving agent (or adhesion imparting agent) of the present invention consists of polysilane. The polysilane may contain at least one structural unit selected from structural units represented by the following formulas (1a) and (1b).

(wherein R ¹ to R ³ each independently represent a hydrogen atom, a hydroxyl group, a halogen atom or an organic group).

In formula (1a), one of R ¹ and R ² may be an alkyl group and the other may be an aryl group. The polysilane may have a weight average molecular weight Mw of about 200-2000.

The adhesion improver may be an adhesion improver for improving adhesion between a resin material and an inorganic material (for example, an adhesive for bonding between a resin material and an inorganic material). The resin material may contain a polyolefin resin, and the inorganic material may contain aluminum, an alloy thereof, or an oxide thereof.

The present invention also includes an adhesive or an adhesive composition containing the adhesion improver (for example, a resin composition containing the adhesion improver and a resin). The adhesive may further contain a thermoplastic resin. The thermoplastic resin may be a polyolefin resin such as a polypropylene resin. The thermoplastic resin may satisfy at least one of the following (i) to (ii).

(i) amorphous; (ii) modified with at least one selected from acids or their anhydrides and epoxy compounds;

In the adhesive or adhesive composition, the proportion of the adhesion improver (polysilane) is about 0.5 to 10% by mass with respect to the total amount of the adhesion improver (polysilane) and the thermoplastic resin. good.

In the present invention, the polysilane is added (for example, to an adhesive, a base material such as a resin base material, a coating agent, etc., preferably by adding the polysilane to the adhesive) to improve the adhesive strength. It also includes a method of improving the (adhesion improving method).

Surprisingly, the adhesion improver comprising the polysilane of the present invention exhibits adhesive strength not only between materials of the same type but also between materials of different types, although the polysilane itself exhibits almost no adhesion. can be improved to In particular, the adhesive force can be effectively improved even when bonding a non-polar substrate and a polar substrate. In addition, even if the substrate (or adherend) is not subjected to pretreatment (or surface treatment) such as roughening treatment or primer treatment, it can be adhered easily (efficiently or with high productivity) with high adhesive strength. .

[Polysilane]
Polysilanes are added to adhesives and/or substrates (particularly to adhesives) to interact with resins in the adhesives or substrates, or to non-polar substrates (e.g., polyolefin resins, etc.). resins with low surface energy (or surface free energy)) - polar substrates (e.g. inorganic materials such as aluminum or its alloys or oxides thereof), even adhesion between dissimilar materials You can effectively improve your strength.

The polysilane may be a chain (linear or branched), cyclic, mesh (or network) compound having Si—Si bonds, and/or a compound having a structure in which two or more of these are combined. Structural units (silane units) constituting polysilane include structural units represented by the following formulas (1a) to (1d) (hereinafter also simply referred to as silane units (1a) to (1d), respectively). ).

(wherein R ¹ to R ⁶ each independently represent a hydrogen atom, a hydroxyl group, a halogen atom or an organic group).

In the above formulas (1a), (1b) and (1d), examples of halogen atoms represented by groups (or side chains) R ¹ to R ⁶ include chlorine atoms.

Examples of organic groups represented by groups (or side chains) R ¹ to R ⁶ include hydrocarbon groups such as alkyl groups, alkenyl groups, cycloalkyl groups, cycloalkenyl groups, aryl groups and aralkyl groups, and hydrocarbon groups thereof. A group in which an ether bond [--O--] is bonded to a hydrogen group, and the like can be mentioned.

Alkyl groups (straight-chain or branched-chain alkyl groups) include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, pentyl and hexyl. linear or branched C _1-14 alkyl groups such as groups, preferably linear or branched C _1-10 alkyl groups, more preferably linear or branched C _{1- 6} alkyl groups.

The alkenyl group includes C _2-14 alkenyl groups such as vinyl group, allyl group, butenyl group and pentenyl group, preferably C _2-6 alkenyl group.

Cycloalkyl groups include C _5-14 cycloalkyl groups such as cyclopentyl, cyclohexyl and methylcyclohexyl groups, preferably C _5-10 cycloalkyl groups.

Cycloalkenyl groups include C _5-14 cycloalkenyl groups such as cyclopentenyl and cyclohexenyl groups, preferably C _5-10 cycloalkenyl groups.

The aryl group includes a C _6-20 aryl group such as a phenyl group and a naphthyl group, preferably a C _6-12 aryl group. The aryl group may have a substituent such as an alkyl group. The number of substituents is not particularly limited, and may be, for example, one or more (eg, 2 to 4), and in the case of more than one, the types of substituents may be the same or different. Examples of the aryl group having such a substituent include C _1-6 alkyl C _6-12 aryl groups such as tolyl group, xylyl group, ethylphenyl group, methylnaphthyl group, etc., preferably mono- to tri- It is a C _1-4 alkyl C _6-10 aryl group, more preferably a mono- or di-C _1-4 alkylphenyl group.

The aralkyl group includes a C _6-20 aryl-C _1-6 alkyl group such as a benzyl group, a phenethyl group and a phenylpropyl group, preferably a C _6-12 aryl-C _1-4 alkyl group. .

The group in which an ether bond [—O—] is bonded to the hydrocarbon group may be a group in which an ether bond is bonded corresponding to the hydrocarbon group exemplified above. Examples include an alkoxy group, a cycloalkyloxy group, Examples include an aryloxy group and an aralkyloxy group.

Examples of alkoxy groups include C _1-14 alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy, t-butoxy, and pentyloxy groups. be done.

Cycloalkyloxy groups include C _5-14 cycloalkyloxy groups such as cyclopentyloxy and cyclohexyloxy groups.

The aryloxy group includes C _6-20 aryloxy groups such as phenoxy group and naphthyloxy group.

The aralkyloxy group includes C _6-20 aryl-C _1-6 alkyloxy groups such as benzyloxy group, phenethyloxy group and phenylpropyloxy group.

Among these groups R ¹ to R ⁶ , hydrogen atoms, hydroxyl groups, alkoxy groups, halogen atoms, etc. are often substituted with terminals such as structural units represented by formula (1d). Generally, the groups R ¹ to R ⁶ are often organic groups, and preferred groups R ¹ to R ⁶ are hydrocarbon groups such as alkyl groups, alkenyl groups, cycloalkyl groups, aryl groups and aralkyl groups, An alkyl group and an aryl group are more preferable in terms of solubility in organic solvents and excellent dispersibility (or compatibility) in resins such as thermoplastic resins (polyolefin resins such as polypropylene resins).

Preferred alkyl groups include linear or branched C _1-4 alkyl groups, more preferably linear or branched C _1-3 alkyl groups, especially methyl group, ethyl group, etc. is a C _1-2 alkyl group of and most preferably a methyl group.

Preferred aryl groups are C _6-12 aryl groups optionally having C _1-4 alkyl such as phenyl group, tolyl group, xylyl group and naphthyl group, more preferably having C _1-3 alkyl. is a C _6-10 aryl group which may have a C 1-2 alkyl group, among which a phenyl group which may have a C _1-2 alkyl group is most preferred.

In formula (1a), R ¹ and R ² preferably contain at least either an alkyl group or an aryl group. Also, the types of R ¹ and R ² may be the same or different, and are preferably different. Typical combinations of R ¹ and R ² include, for example, combinations of alkyl groups, combinations of aryl groups, combinations of alkyl groups and aryl groups, and the like.

The combination of alkyl groups includes, for example, a combination of linear or branched C _1-4 alkyl groups, preferably a combination of linear or branched C _1-3 alkyl groups. more preferably a combination of methyl groups or ethyl groups, particularly a combination of methyl groups.

The combination of aryl groups includes, for example, a combination of C _6-12 aryl groups optionally having C _1-4 alkyl, preferably having C _1-2 alkyl. It is a combination of phenyl groups, more preferably a combination of phenyl groups.

A combination of an alkyl group and an aryl group may be such that one of R ¹ and R ² is an alkyl group and the other is an _aryl group. and a C _6-12 aryl group optionally having C _1-4 alkyl, preferably having a linear or branched C _1-3 alkyl group and a C _1-2 alkyl It is a combination with a phenyl group that may be present.

These silane units (1a) having a combination of R ¹ and R ² may be contained singly or in combination of two or more. Among these combinations of R ¹ and R ² , combinations of aryl groups or combinations of alkyl groups and aryl groups are preferable, and solubility in organic solvents and thermoplastic resins (polyolefin resins such as polypropylene resins, etc.) ) and the like, the combination of an alkyl group and an aryl group is preferable, more preferably a methyl group or an ethyl group and a phenyl group or a mono- or di-C _1-2 alkylphenyl groups, and a combination of a methyl group and a phenyl group is particularly preferred.

Also, in formula (1b), R ³ is often an alkyl group or an aryl group. Preferred embodiments of the alkyl group or aryl group are the same as the above preferred alkyl group and preferred aryl group. These silane units (1b) may be contained alone or in combination of two or more. Of these silane units (1b), ^R3 is preferably an aryl group, particularly preferably a phenyl group.

In formula (1d), the types of R ⁴ to R ⁶ may be the same or different. At least part of the terminal groups of the polysilane may be an alkyl group, an aryl group, or a silanol group (where R ⁴ to R ⁶ are hydroxyl groups). When the terminal group is a silanol group (hydroxyl group), the mechanical strength, adhesive strength (or peel strength) can be improved.

Generally, polysilane often has at least one structural unit among the structural units represented by formulas (1a) and (1b).

The total ratio of silane units (1a) and silane units (1b) to the entire polysilane can be selected from a wide range of 10 to 100 mol%, for example 30 mol% or more (eg 40 to 90 mol%), preferably 50 mol%. or more (eg, 60 to 85 mol%), more preferably 70 mol% or more (eg, 75 to 80 mol%), more preferably 90 mol% or more, usually 40 to 90 mol%, preferably 50 ~80 mol%, more preferably 55 to 75 mol%, especially 60 to 70 mol%.

The ratio of the silane units (1a) and the silane units (1b) can be selected from a wide range of, for example, the former/latter (molar ratio)=10/90 to 100/0, for example, 50/50 to 100/0 (for example, 55/45 to 90/10), preferably 60/40 to 100/0 (eg 65/35 to 85/15), more preferably 70/30 to 100/0 (eg 75/25 to 80/20) or only the silane unit (1) may be (100/0).

The ratio of the silane units (1b) to the total polysilane may be, for example, about 0 to 20 mol % (eg, 1 to 10 mol %, preferably 2 to 5 mol %).

The ratio of silane units (1c) to the total polysilane may be, for example, about 0 to 20 mol % (eg, 1 to 10 mol %, preferably 2 to 5 mol %).

The ratio of the silane units (1d) to the total polysilane may be, for example, about 0 to 40 mol % (eg, 1 to 20 mol %, preferably 5 to 10 mol %).

Among silane units, the polysilane preferably contains at least a structural unit represented by formula (1a). Therefore, the ratio of the silane units (1a) to the entire polysilane may be, for example, about 10 to 99 mol%, preferably 30 to 95 mol%, more preferably 40 to 90 mol%, still more preferably 50 to 80 mol%. mol %, especially 55 to 75 mol %, especially 60 to 70 mol %.

When the polysilane contains structural units represented by formulas (1a) and (1d) such as linear polysilane, the ratio of the silane units (1a) and the silane units (1d) is, for example, the former/latter (mol ratio) = about 10/90 to 99/1, preferably 30/70 to 95/5, more preferably 40/60 to 90/10, still more preferably 50/50 to 80/20, especially However, it is 55/45 to 75/25, especially 60/40 to 70/30.

The polymerization form of the polysilane is not particularly limited, and may be a homopolymer or a copolymer such as a random copolymer, a graft copolymer, a block copolymer, or an alternating copolymer.

Typical polysilanes include, for example, linear or cyclic polysilanes having at least silane units (1a), branched or network polysilanes having at least silane units (1b) and/or silane units (1c) (e.g., network polysilane) and the like.

Examples of linear or cyclic polysilanes having silane units (1a) include polydialkylsilanes, polyalkylarylsilanes, polydiarylsilanes, dialkylsilane-alkylarylsilane copolymers, alkylarylsilane-diarylsilane copolymers, Examples thereof include dialkylsilane-diarylsilane copolymers.

Examples of polydialkylsilane include polydi-C _1- silane such as polydimethylsilane, polymethylpropylsilane, polymethylbutylsilane, polymethylpentylsilane, polydibutylsilane, polydihexylsilane, and dimethylsilane-methylhexylsilane copolymer. _8- alkylsilane, etc., preferably poly-di-C _1-4 alkylsilane, more preferably poly-di-C _1-2 alkylsilane.

Examples of polyalkylarylsilanes include poly(C _1-8 alkyl-C _6-12 arylsilanes) such as polymethylphenylsilane and methylphenylsilane-phenylhexylsilane copolymers, preferably poly( C _1-4 alkyl-C _6-10 arylsilane), more preferably poly(C _1-2 alkyl-phenylsilane).

Polydiarylsilanes include, for example, polydiC _6-12 arylsilanes such as polydiphenylsilane, preferably polydiC _6-10 arylsilanes, more preferably polydiphenylsilanes.

Dialkylsilane-alkylarylsilane copolymers include, for example, di-C _1-8 copolymers such as dimethylsilane-methylphenylsilane copolymers, dimethylsilane-hexylphenylsilane copolymers, and dimethylsilane-methylnaphthylsilane copolymers. alkylsilane-(C _1-8 alkyl-C _6-12 arylsilane) copolymers, preferably di-C _1-4 alkylsilane-(C _1-4 alkyl-C _6-10 arylsilane) copolymers. Polymers, more preferably di-C _1-2 alkylsilane-(C _1-2 alkyl-phenylsilane) copolymers.

Examples of alkylarylsilane-diarylsilane copolymers include (C _1-8 alkyl-C _6-12 arylsilane)-diC _6-12 arylsilane copolymers such as methylphenylsilane-diphenylsilane copolymers. and the like, preferably (C _1-4 alkyl-C _6-10 arylsilane)-diC _6-10 arylsilane copolymer, more preferably (C _1-2 alkyl-phenylsilane)-diphenylsilane copolymer It is a polymer.

Examples of dialkylsilane-diarylsilane copolymers include di-C _1-8 alkylsilane-di-C _6-12 arylsilane copolymers such as dimethylsilane-diphenylsilane copolymers, preferably di-C It is _{a 1-4} alkylsilane-diC _6-10 arylsilane copolymer, more preferably a di-C _1-2 alkylsilane-diphenylsilane copolymer.

Examples of branched or network-like polysilanes (eg, network-like polysilanes) having silane units (2b) include polyalkylsilanes and polyarylsilanes.

Examples of polyalkylsilanes include polyC _1-8 alkylsilanes such as polymethylsilane, polypropylsilane, polybutylsilane, and polyhexylsilane, preferably polyC _1-4 alkylsilanes, and more preferably polyC 1-4 alkylsilanes. It is a poly C _1-2 alkylsilane.

Polyarylsilanes include, for example, polyC _6-12 arylsilanes such as polyphenylsilanes, preferably polyC _6-10 arylsilanes, and more preferably polyphenylsilanes.

These polysilanes can be used alone or in combination of two or more. Among these polysilanes, the silane unit (1a) is at least preferably linear or cyclic polysilanes, more preferably polyalkylarylsilanes and polydiarylsilanes, still more preferably linear polyalkylarylsilanes and cyclic polydiarylsilanes (for example, cyclic polysilanes such as decaphenylcyclopentasilane). PolydiC _6-10 arylsilanes, etc.), among which linear polyalkylarylsilanes such as linear poly(C _1-4 alkyl-C _6-10 arylsilanes) are preferred, especially linear polymethyl Linear poly(C _1-2 alkyl-phenylsilanes) such as phenylsilanes.

The polysilane preferably has no siloxane bonds (--Si--O--Si--), but may inevitably have a small amount of siloxane bonds.

The average degree of polymerization of polysilane, in terms of silicon atoms (that is, the average number of silicon atoms per molecule), may be, for example, about 500 or less, specifically about 2 to 250, preferably 3 to 100, More preferably 3.5 to 50, still more preferably 4 to 20, especially 4.5 to 10, especially 5 to 7. If the average degree of polymerization is too high, the solubility in solvents and the dispersibility (or compatibility) in the resin component contained in the adhesive and/or the base material (adherend) may decrease. On the other hand, if the average degree of polymerization is too small, there is a possibility that the adhesiveness cannot be improved.

The weight average molecular weight Mw of the polysilane can be selected from a range of, for example, 100 or more, specifically about 150 to 50,000, for example, 200 to 30,000 (for example, 250 to 20,000), preferably 300, in a measurement method by GPC (converted to polystyrene). ~15000 (eg 350 to 10000), more preferably 400 to 5000 (eg 450 to 3000). Generally, it may be about 200 to 2000, preferably 500 to 1500 (eg 550 to 1000), particularly preferably 600 to 800 (eg 650 to 750).

The number average molecular weight Mn of the polysilane is, for example, about 30,000 or less, for example, 100 to 10,000, preferably 300 to 3,000, more preferably 400 to 1,000 (especially 500 to 700), as measured by GPC (converted to polystyrene). .

The dispersity Mw/Mn is, for example, 1 to 5, preferably 1 to 3, more preferably 1 to 2, especially 1 to 1.5.

If the weight-average molecular weight Mw or number-average molecular weight Mn is too large, the solubility in solvents and the dispersibility (or compatibility) in resin components contained in adhesives may decrease. The weight average molecular weight Mw, number average molecular weight Mn, and degree of dispersion Mw/Mn of polysilane can be measured by GPC in terms of standard polystyrene.

Polysilane may be liquid (or viscous) or solid at room temperature (for example, about 20° C.). It is preferably liquid (or viscous) from the viewpoint of dispersibility (or compatibility) with respect to such as.

A commercially available product may be used as the polysilane, or it may be prepared. In the case of preparation, a conventional method such as a preparation method using halosilanes having structural units represented by the above formulas (1a) to (1d) may be used. For example, the halosilanes are dehalogenated using magnesium as a reducing agent. condensation polymerization method (“Magnesium reduction method”, WO98/29476, etc.), method of dehalogen condensation polymerization of halosilanes in the presence of an alkali metal (“Kipping method”, J.Am.Chem.Soc., 110, 124). (1988), Macromolecules, 23, 3423 (1990), etc.), a method of dehalogen condensation polymerization of halosilanes by electrode reduction (J. Chem. Soc., Chem. Commun., 1161 (1990), J. Chem. Soc. ., Chem. Commun. 897 (1992), etc.), a method of dehydrogenative condensation polymerization of hydrosilanes in the presence of a metal catalyst (JP-A-4-334551, etc.), an anionic polymerization of disilene crosslinked with biphenyl, etc. (Macromolecules, 23, 4494 (1990), etc.), ring-opening polymerization of cyclic silanes, and the like.

Such polysilanes can be used singly or in combination of two or more as an adhesion improving agent (or adhesion imparting agent). The adhesion improver is not particularly limited as long as the application requires adhesion (or adhesion), and the object to be added is not particularly limited. Resin base material formed of curable resins, thermoplastic resins, etc. exemplified in the resin component section of adhesives], coating agents (coating films or paints), etc. to improve adhesion (or adhesion) may be improved, preferably added to the adhesive to improve adhesion.

The proportion when adding polysilane is, for example, 0.001 to 80% by mass with respect to the total solid content to be added (when added to adhesives, coating agents, etc., the total active ingredients (components excluding solvents)). may be about, and the preferred range is, stepwise, 0.01 to 50% by mass, 0.05 to 30% by mass, 0.1 to 15% by mass, 0.5 to 10% by mass, 1 ~9% by mass, 2-8% by mass, 3-7% by mass, 4-6% by mass. If the proportion of polysilane is too low, there is a possibility that the adhesive strength cannot be improved. Moreover, even if the proportion of polysilane is too high, there is a possibility that the adhesive strength cannot be improved. In the present invention, even if the amount of polysilane added is relatively small, the adhesion can be effectively improved. Therefore, the physical properties of the material before the addition of polysilane can be effectively maintained without significantly deteriorating.

The peel strength (or adhesive strength) when polysilane is added is the same as when polysilane is not added. 1.3 to 10 times, preferably 1.5 to 5 times, more preferably 2 to 3.5 times, compared to the case). In the present specification and claims, the peel strength can be measured by a 180° peel test described in Examples below.

[glue]
The adhesion improver (polysilane) of the present invention can be used particularly effectively as an additive for improving the adhesive strength of adhesives. The reason for this is not clear, but although polysilane exhibits properties such as releasability and antifouling properties (or water repellency), unexpectedly, the resin component (or adhesive component) contained in the adhesive ), it seems that a higher effect of improving adhesiveness is exhibited even for adhesion between different materials such as between a non-polar substrate and a polar substrate. Therefore, the adhesive should just contain at least polysilane and a resin component.

(resin component)
The resin component (or adhesive component) contained in the adhesive may be a conventional resin used as an adhesive and/or a pressure-sensitive adhesive, such as a curable resin such as a phenolic resin (resol-type phenolic resin, novolak type phenolic resin, etc.), amino resin (urea resin, melamine resin, guanamine resin, etc.), furan resin, unsaturated polyester resin, diallyl phthalate resin, vinyl ester resin (or epoxy (meth)acrylate resin), polyfunctional (meth) Acrylate resins, epoxy resins, urethane resins, polyimide resins (such as bismaleimide resins), silicone resins, and the like may be used, but thermoplastic resins are preferred because they can be easily and effectively bonded with high adhesive strength.

Examples of thermoplastic resins include polyolefin resins (chain olefin resins such as polyethylene resins and polypropylene resins, cyclic olefin resins, etc.); styrene resins [polystyrene (PS) {general-purpose polystyrene (GPPS), syndiotactic polystyrene (SPS), etc.}; system copolymer {high-impact polystyrene (HIPS), acrylonitrile-butadiene-styrene copolymer (ABS resin), AXS resin (acrylonitrile-acrylic rubber-styrene copolymer (AAS resin), acrylonitrile-chlorinated polyethylene-styrene copolymer (ACS resin), acrylonitrile-(ethylene-propylene-diene rubber)-styrene copolymer (AES resin), etc.), methyl methacrylate-butadiene-styrene copolymer (MBS resin), etc.], etc.]; (Meth)acrylic resins [polymethyl methacrylate (PMMA), (meth)acrylic acid-(meth)acrylic acid ester copolymers such as (meth)acrylic monomers or copolymers]; vinyl acetate -based resin [polyvinyl acetate (PVAc), polyvinyl alcohol (PVA), polyvinyl acetal (polyvinyl formal (PVF), polyvinyl butyral (PVB), etc.)]; vinyl chloride resin [vinyl chloride resin (vinyl chloride homopolymer ( PVC); vinyl chloride copolymer such as vinyl chloride-vinyl acetate copolymer, etc.), vinylidene chloride resin (vinylidene chloride-vinyl chloride copolymer such as vinylidene chloride-vinyl chloride copolymer, vinylidene chloride-acrylonitrile copolymer, etc.) etc.]; fluorine resin [polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), tetrafluoroethylene-hexafluoropropylene copolymer (FEP ), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), ethylene-tetrafluoroethylene copolymer (ETFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), etc.]; polyester resin [polyalkylene arylate resin (polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), poly 1,4-cyclohexyldimethylene terephthalate (PCT), polyethylene naphthalate, etc.), polyarylate resin, liquid crystal polyester (LCP), etc.]; polycarbonate resin (PC) [bisphenol type polycarbonate resin such as bisphenol A type polycarbonate resin]; polyamide resin (PA) [aliphatic polyamide resin (polyamide 6, polyamide 66, etc.), aromatic polyamide resin or Aramid resin (poly m-phenylene isophthalamide, poly p-phenylene terephthalamide, etc.)]; polyacetal resin (POM); polyphenylene ether resin (PPE); polyether ketone resin [polyether ketone resin (PEK), polyether ether ketone resin (PEEK), polyether ketone ether ketone ketone (PEKEKK), etc.); phenoxy resin; polyketone resin (aliphatic polyketone resin, etc.); polyphenylene sulfide resin (PPS); ether sulfone resin (PES), etc.); cellulose derivative [cellulose ester (nitrocellulose, cellulose acetate, cellulose acetate propionate, etc.), cellulose ether (ethyl cellulose, etc.), etc.]; thermoplastic polyimide resin (polyetherimide (PEI), polyamideimide, etc.); polyethernitrile resin; thermoplastic elastomer (TPE) [polystyrene TPE, polyolefin TPE (TPO), polydiene TPE, chlorine TPE, fluorine TPE, polyurethane TPE (TPU), polyester TPE (TPEE), polyamide-based TPE (TPA), etc.] and the like.

These resins (especially thermoplastic resins) may be contained alone or in combination of two or more. Among these resins (especially thermoplastic resins), amorphous (or low-crystalline) and/or solvent-soluble resins are preferable from the viewpoint of adhesion, and amorphous (or low-crystalline) It is more preferable to have As specific resins, polyolefin resins, (meth)acrylic resins, vinyl acetate resins, vinyl chloride resins, polyamide resins (PA), cellulose derivatives, and thermoplastic elastomers (TPE) are preferred. Polyolefin-based resins are more preferable because they can more effectively improve adhesive strength even when used for adhesion to polar substrates.

Examples of polyolefin resins include linear olefin resins containing α-olefin as a main polymerization component, and cyclic olefin resins containing cyclic olefins as polymerization components. Cyclic olefin resins include cyclic olefin copolymers (COC) such as ethylene-norbornene copolymers, addition or development of cyclic olefins such as polynorbornene, polydicyclopentadiene, polycyclopentadiene, or hydrogenated products thereof. A ring polymer or a hydrogenated product thereof may be mentioned. These polyolefin resins may be used alone or in combination of two or more. Among these polyolefin resins, chain olefin resins are usually used in many cases.

Examples of α-olefins that are polymerization components of chain olefin resins include ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-heptene, 4-methyl-1-hexene, 4,4-dimethyl-1-pentene, 3-ethyl-1-pentene, 1-octene, 4,4-dimethyl-1- α-C _2-20 olefins such as hexene, 3-ethyl-1-hexene, 4-ethyl-1-hexene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene etc., preferably α-C _2-10 olefins, more preferably α-C _2-6 olefins such as ethylene and propylene.

The chain olefin-based resin may be a homopolymer or a copolymer of the α-olefin. Polymer components in the copolymer may contain two or more α-olefins, and may contain copolymerizable monomers different from α-olefins. Note that the copolymer may be a random copolymer, a block copolymer, a graft copolymer, or the like.

Examples of copolymerizable monomers different from the α-olefin include (meth)acrylic monomers, unsaturated carboxylic acids or their acid anhydrides, carboxylic acid vinyl esters, and dienes.

Examples of (meth)acrylic monomers include (meth)acrylic acid, (meth)acrylic acid esters, (meth)acrylamides, N-substituted (meth)acrylamides, and (meth)acrylonitrile. Examples of the (meth)acrylic ester include alkyl (meth)acrylate and glycidyl (meth)acrylate. Examples of the alkyl (meth)acrylate include methyl (meth)acrylate, , (meth)acrylic acid C _1-10 alkyl esters such as ethyl (meth)acrylate. Examples of the N-substituted (meth)acrylamides include mono- or dialkyl(meth)acrylamides such as N,N-dimethyl(meth)acrylamide and N-isopropyl(meth)acrylamide.

Examples of unsaturated carboxylic acids or acid anhydrides thereof include (meth)acrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, mesaconic acid, angelica acid and their anhydrides (anhydrous maleic acid, etc.).

Carboxylic acid vinyl esters include saturated carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate.

Examples of dienes include non-conjugated alkadienes such as 1,4-hexadiene, 1,7-octadiene, 4-methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene, and conjugated alkadienes such as butadiene and isoprene. etc.

These copolymerizable monomers can be used alone or in combination of two or more. When the linear olefin resin (eg, polypropylene resin) contains a copolymerizable monomer, the ratio of the copolymerizable monomer to the total structural units may be, for example, about 70 mol% or less. 50 mol% or less, for example 30 mol% or less (eg 0.01 to 30 mol%), preferably 20 mol% or less (eg 0.1 to 20 mol%), more preferably 10 mol% or less (eg 1 to 10 mol%) mol%).

Typical linear olefin resins include polyethylene resins, polypropylene resins, poly-1-butene-based resins, poly-α- _C2-6 olefin-based resins such as poly-4-methyl-1-pentene-based resins, and the like. mentioned. These polyolefin resins can be used alone or in combination of two or more.

Among these polyolefin resins, polyethylene resins [e.g., low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear low density polyethylene (LLDPE), ultra high molecular weight Polyethylene (UHMWPE), ethylene-(α- _C4-10 olefin) copolymer [ethylene-(1-butene) copolymer, ethylene-(4-methyl-1-pentene) copolymer, etc.], modified polyethylene (maleic anhydride-modified polyethylene, etc.), chlorinated polyethylene, ionomer, etc.] and polypropylene-based resins are often used, and polypropylene-based resins are particularly preferred.

Polypropylene resins include, for example, polypropylene (or propylene homopolymer); copolymers or modified polypropylenes of propylene and other copolymerizable monomers, specifically propylene-ethylene copolymers, propylene-( 1-butene) copolymer, copolymers of propylene and other α- _C2-10 olefins such as propylene-ethylene-(1-butene) copolymer, maleic anhydride-modified polypropylene, chlorinated polypropylene, etc. mentioned. In the copolymer of propylene and other α-C _2-10 olefin, the proportion of propylene (or propylene units) is, for example, 70 mol% or more (for example, 75 to 99.5 mol%) with respect to the total monomer. ), preferably 80 mol % or more (eg, 85 to 99 mol %), more preferably 90 mol % or more (eg, 94 to 98 mol %).

In addition, from the viewpoint of crystallinity, polypropylene-based resins include high-density polypropylene (high-crystalline polypropylene (HCPP)), medium-density polypropylene, low-density polypropylene (low-crystalline polypropylene (LCPP)), ultra-low-density polypropylene (ultra-low crystalline polypropylene (VLCPP)) and the like. From the viewpoint of stereoregularity, the polypropylene resin may be a polypropylene resin having stereoregularity such as isotactic polypropylene (IPP) and syndiotactic polypropylene (SPP). It may also be a polypropylene-based resin that does not have stereoregularity. The polypropylene-based resin having stereoregularity may be a polypropylene-based resin having a narrow molecular weight distribution obtained using a metallocene catalyst.

These polypropylene resins may be used alone or in combination of two or more. The polypropylene-based resin may be a crystalline polypropylene-based resin, but from the viewpoint of adhesion, an amorphous (or low-crystalline) polypropylene-based resin (for example, propylene-(1-butene) copolymer, etc.) Copolymers of propylene with other α-C _2-10 olefins, LCPP, VLCPP, APP, etc.) or maleic anhydride modified polypropylene are preferred. Combining polysilane with such a polypropylene-based resin seems to be able to improve adhesion more effectively.

Therefore, the thermoplastic resin (especially polyolefin resin such as polypropylene resin) preferably satisfies at least one of the following (i) to (ii) from the viewpoint of further improving adhesion, especially at least (ii). preferably fulfilled.

(i) amorphous (or low crystallinity); (ii) modified with at least one selected from acids (such as unsaturated carboxylic acids) or their anhydrides, and epoxy compounds;

Regarding (i) above, the crystallinity of the amorphous (or low-crystalline) thermoplastic resin (especially the amorphous polypropylene resin) may be, for example, about 50% or less, preferably 30% or less. , more preferably 10% or less, particularly substantially about 0% (perfectly amorphous).

Regarding the above (ii), the acid or acid anhydride for modifying (acid modification) or grafting the thermoplastic resin (especially polyolefin resin such as polypropylene resin) includes, for example, the above-mentioned α-olefin Different copolymerizable monomers include compounds similar to the acids or anhydrides thereof exemplified as unsaturated carboxylic acids or acid anhydrides thereof, preferably (meth)acrylic acid, maleic acid or anhydride thereof, More preferred is maleic acid or its anhydride.

As the epoxy compound for modifying (epoxy-modified or glycidyl-modified) or grafting the thermoplastic resin (especially polyolefin resin such as polypropylene resin), an ethylenically unsaturated bond and an epoxy-containing group (epoxy group, glycidyl group, 2-methylglycidyl group, cyclohexenyl oxide group (epoxidized cyclohexenyl group), etc.), and specific examples include glycidyl (meth)acrylate.

The ratio of the acid or its anhydride and the epoxy compound (modified ratio or modified amount) is, for example, 30% by mass or less (for example, 0.5 to 25% by mass), preferably 20%, based on the entire modified thermoplastic resin. % or less (for example, 1 to 15% by mass).

Of acid or its anhydride and epoxy compound, modification with at least acid or its anhydride is preferred, and modification with acid anhydride is particularly preferred.

The acid value of a thermoplastic resin modified (acid-modified) with an acid (unsaturated carboxylic acid or the like) or its anhydride (especially an acid-modified polyolefin resin such as maleic anhydride-modified polypropylene) is, for example, 0.1 to 250 mgKOH/ gram, preferably 1 to 200 mgKOH/g, more preferably 10 to 100 mgKOH/g.

Further, the weight average molecular weight Mw of the thermoplastic resin (especially polyolefin resin such as polypropylene resin) may be selected from a range of about 1000 to 10000000, for example. Also, the number average molecular weight Mn may be selected from a range of, for example, about 1,000 to 1,000,000. The molecular weight distribution Mw/Mn may be selected from a range of about 1-50, for example, 2-25. If the weight-average molecular weight Mw or the number-average molecular weight Mn is too large, the adhesiveness may deteriorate, and if it is too small, the mechanical strength (or durability) may deteriorate. In the present specification and claims, the weight average molecular weight, number average molecular weight and molecular weight distribution can be measured by GPC in terms of standard polystyrene.

The melting point of thermoplastic resins (especially polyolefin resins such as polypropylene resins) may be, for example, about 30 to 200° C. (eg, 35 to 180° C.), preferably 40 to 150° C. (eg, 45 to 120° C.). , more preferably 50 to 100° C. (eg, 55 to 90° C.), especially 60 to 80° C., and may not have a melting point.

The ratio of the adhesion improver (polysilane) contained in the adhesive is, for example, the total amount of the adhesion improver (polysilane) and resin components such as thermoplastic resins (especially polyolefin resins such as polypropylene resins). It may be about 0.001 to 80% by mass, and preferable ranges are 0.01 to 50% by mass, 0.05 to 30% by mass, 0.1 to 15% by mass, 0.01 to 50% by mass, 0.05 to 30% by mass, 0.1 to 15% by mass, and 0.001 to 50% by mass. 5 to 10% by mass, 1 to 9% by mass, 2 to 8% by mass, 3 to 7% by mass, and 4 to 6% by mass. If the proportion of polysilane is too low, the adhesive strength of the adhesive may not be improved. Also, if the proportion of polysilane is too high, the adhesive strength of the adhesive may not be improved. In the present invention, the adhesion can be effectively improved even with a relatively small proportion of polysilane. Therefore, the physical properties of the material before the addition of polysilane can be effectively maintained without significantly deteriorating.

(other ingredients)
Depending on the type of resin component, adhesive form (e.g., solvent type, hot melt type, emulsion type, latex type, etc.), application, etc., if necessary, a solvent (solvent or dispersion medium) or Other ingredients such as conventional additives may be included.

Examples of solvents (solvents or dispersion media) include hydrocarbons, halogenated hydrocarbons, alcohols, ethers, glycol ethers, glycol ether acetates, ketones, carboxylic acids, esters, carbonates, amides, ureas, nitriles, nitrated hydrocarbons, phosphoramides, sulfones, sulfoxides, water and the like.

Hydrocarbons include aliphatic hydrocarbons such as hexane and dodecane, alicyclic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as toluene and xylene, mineral spirits, and petroleum-based mixed solvents such as solvent naphtha. is mentioned.

Halogenated hydrocarbons include, for example, dichloromethane, chloroform, 1,2-dichloroethane, chlorobenzene, dichlorobenzene and the like.

Alcohols include C _1-6 alcohols such as methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, s-butanol and t-butanol.

Ethers include chain ethers, cyclic ethers, and the like. Examples of chain ethers include di-C _1-6 alkyl ethers such as diethyl ether, diisopropyl ether and dibutyl ether. Cyclic ethers include tetrahydrofuran (THF), 2-methyltetrahydrofuran, tetrahydropyran, 4-methyltetrahydropyran, 1,4-dioxane, 1,3-dioxane, 4-methyl-1,3-dioxane, 1,3 -dioxolane, 5- to 7-membered ring ethers such as 2-methyl-1,3-dioxolane, and the like.

Examples of glycol ethers include (poly)alkylene glycol monoalkyl ethers and (poly)alkylene glycol dialkyl ethers. (Poly)alkylene glycol monoalkyl ethers include, for example, cellosolves such as methyl cellosolve and ethyl cellosolve, carbitols such as methyl carbitol and ethyl carbitol, triethylene glycol monomethyl ether, propylene glycol monomethyl ether and dipropylene glycol. and (mono- to hexa-)C _2-4 alkylene glycol mono-C _1-6 alkyl ethers such as monomethyl ether. Examples of (poly)alkylene glycol dialkyl ether include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and the like. (mono to hexa)C _2-4 alkylene glycol di-C _1-6 alkyl ether of

Glycol ether acetates include, for example, cellosolve acetates such as methyl cellosolve acetate, carbitol acetates such as methyl carbitol acetate, propylene glycol monomethyl ether acetate (PGMEA), dipropylene glycol monobutyl ether acetate and the like (poly)C _2-4 alkylene glycol mono C _1-4 alkyl ether acetate and the like.

Examples of ketones include chain ketones such as acetone, methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK); and cyclic ketones such as cyclohexanone.

Examples of carboxylic acids include acetic acid and propionic acid.

Examples of esters include chain esters and cyclic esters. Examples of chain esters include acetic acid esters such as methyl acetate, ethyl acetate and butyl acetate, and lactic acid esters such as methyl lactate. Cyclic esters (or lactones) include 5- to 7-membered ring lactones optionally having substituents such as γ-butyrolactone, γ-valerolactone, γ-caprolactone (or γ-hexanolactone), and the like. mentioned.

Carbonates include chain carbonates, cyclic carbonates and the like. Examples of chain carbonates include di-C _1-6 alkyl-carbonates such as dimethyl carbonate (or dimethyl carbonate), ethylmethyl carbonate, diethyl carbonate (or diethyl carbonate), and the like. Examples of cyclic carbonates include 5- to 7-membered ring carbonates such as ethylene carbonate (or ethylene carbonate) and propylene carbonate (or propylene carbonate).

Amides include chain amides, cyclic amides (or lactams), and the like. Examples of chain amides include N,N-diC _1-6 alkyl-C ₁ such as N,N-dimethylformamide (DMF), N,N-diethylformamide and N,N-dimethylacetamide (DMAc). _-6 alkanoic acid amide and the like. Cyclic amides include, for example, 5- to 7-membered ring lactams such as N-methyl-2-pyrrolidone (NMP).

Examples of ureas (or ureas) include chain ureas and cyclic ureas. Chain ureas include, for example, tetra-C _1-6 alkyl-ureas such as tetramethylurea, tetraethylurea and tetraisopropylurea. Examples of cyclic ureas include 1,3-dimethyl-2-imidazolidinone (DMI or N,N'-dimethylethylene urea), N,N'-dimethyl-N,N'-trimethylene urea (or N, N,N'-diC _1-6 alkyl-N,N'-di to tetramethylene urea such as N'-propylene urea).

Nitriles include, for example, C _1-6 alkane cyanides such as acetonitrile and propionitrile, and arene cyanides such as benzonitrile.

Examples of nitrated hydrocarbons include nitroC _1-6 alkanes such as nitromethane, nitroethane, 1-nitropropane and 2-nitropropane, and nitroarenes such as nitrobenzene.

Phosphoramides include, for example, hexaC _1-6 alkylphosphoramides such as hexamethylphosphoramide.

Examples of sulfones include chain sulfones and cyclic sulfones. Examples of chain sulfones include di-C _1-6 alkyl sulfones such as ethylmethylsulfone and isopropylethylsulfone. Cyclic sulfones include, for example, sulfolane (or tetramethylene sulfone or tetrahydrothiophene-1,1-dioxide), tri- to hexamethylene sulfones such as 3-methylsulfolane and 2,4-dimethylsulfolane.

Sulfoxides include, for example, di-C _1-6 alkylsulfoxides such as dimethylsulfoxide (DMSO).

These solvents may be contained alone or in combination of two or more. Among these solvents, hydrocarbons (aromatic hydrocarbons such as toluene and xylene, petroleum mixed solvents such as mineral spirits, etc.), halogenated hydrocarbons, etc. (such as chloroform), ethers (such as cyclic ethers such as THF), glycol ether acetates (such as (poly)C _2-4 alkylene glycol mono-C _1-4 alkyl ether acetate such as PGMEA), ketones (MEK chain ketones such as cyclohexanone, cyclic ketones such as cyclohexanone, etc.), esters (acetic acid esters such as ethyl acetate, etc.), amides (cyclic amides such as NMP, etc.), etc., are often used. are often aromatic hydrocarbons.

The amount of the solvent to be used is not particularly limited, and may be an amount that can be adjusted to the desired viscosity, and may be solvent-free. When a solvent is used, the solid content concentration of the adhesive (concentration of active ingredient (component excluding solvent)) is, for example, 1 to 90% by mass (eg, 3 to 70% by mass), preferably 5 to 50% by mass (eg, 8 to 30% by mass), more preferably about 10 to 15% by mass.

Examples of the conventional additives include fillers (reinforcing agents or reinforcing agents) (granular or fibrous fillers, etc.), stabilizers (antioxidants, antiozonants, ultraviolet absorbers, light stabilizers, , heat stabilizers, weather stabilizers, etc.), tackifiers (tackifiers), other adhesion improvers different from the adhesion improver of the present invention (adhesion improvers), plasticizers, softeners, hardeners , colorants (dyes, pigments, etc.), flame retardants, flame retardant aids, antistatic agents, conductive agents, rust inhibitors, surfactants, flow control agents, leveling agents, antifoaming agents, surface modifiers (silane coupling agents, etc.), dispersants, compatibilizers, and the like.

These additives may be used alone or in combination of two or more. The proportion of the additive is, for example, 30 parts by mass or less (eg, 0 to 20 parts by mass), preferably 10 parts by mass or less (eg, 0 to 5 parts by mass).

[Base material (adherend or adherend)]
The type of two or more substrates to be adhered (or bonded) to each other with or without an adhesive (preferably with an adhesive) is not particularly limited. Examples of the material forming the substrate (especially the surface of the substrate or the adhesive surface) include resin materials (for example, resins similar to the curable resins and thermoplastic resins exemplified in the section of the resin component of the adhesive, rubber, wood, etc.), inorganic materials (eg, metals such as elemental metals and alloys; glass, silicon, cement, ceramics such as metal oxides, etc.).

Examples of the metal element include magnesium, aluminum, titanium, chromium, iron, nickel, copper, and zinc. Examples of the alloy include an alloy containing the metal element, specifically an aluminum alloy. , steel (stainless steel, high-strength steel, ultra-high-strength steel, etc.). Examples of the metal oxide include oxides of the metals exemplified as the metal element (or alloy), and specific examples include aluminum oxide (alumina), titanium oxide (titania, etc.), iron oxide, and the like. be done.

These materials can be used alone or in combination of two or more to form the substrate (one substrate). In the present invention, it is possible to effectively bond not only materials of the same type but also materials of different types. Therefore, it is preferable that the bonding surfaces of at least two substrates are made of different materials, particularly resin materials. - Adhesion between inorganic materials (adhesion between a substrate whose adhesion surface mainly contains a resin material and a substrate whose adhesion surface mainly contains an inorganic material) is preferred.

In the present specification and claims, "mainly containing" means that it is the main component (or the largest component) in the constituent components, and the entire constituent components of the adhesive surface (substrate surface) , for example, 50% by mass or more (e.g., 60% by mass or more), preferably 70% by mass or more (e.g., 80% by mass or more), more preferably 90% by mass or more (e.g., 95% by mass or more). do.

In bonding such resin materials and inorganic materials, preferred resin materials include resins having low surface energy (non-polar resins) such as polyolefin resins, and more preferably polyethylene resins and polypropylene resins. Yes, especially polypropylene resin. Preferred inorganic materials include elemental metals, alloys thereof, or oxides thereof, more preferably aluminum, alloys thereof, or oxides thereof, and particularly oxides of aluminum or an alloy thereof. In the present invention, even non-polar substrates made of non-polar resins (especially polyolefin resins such as polypropylene resins), which are difficult to bond even between materials of the same kind, can be applied to inorganic materials (especially aluminum or its alloys or It can be easily adhered to a polar substrate formed of oxides thereof, etc., with high adhesive strength.

In the present specification and claims, the term “polar substrate” refers to the presence of polar groups (oxygen-containing groups such as hydroxyl groups, carboxyl groups, etc.), so that non-polar resins such as polyolefin resins can be used. It means a base material having a higher surface energy than the base material, and not only base materials made of inorganic materials such as metals and metal oxides, but also polar resins such as polyester resins such as PET and polycarbonate resins such as bisphenol type polycarbonate. , polyamide resins such as aliphatic polyamide resins, and base materials formed of styrene resins containing acrylonitrile as a copolymerization component such as ABS resins.

The substrate may be pretreated (or surface treated) as necessary. The surface treatment is not particularly limited, and may be a treatment for changing the composition and/or shape of the substrate surface, a treatment for coating the substrate surface with a material different from that of the substrate, or the like. For example, corona discharge treatment, chromic acid treatment, ozone and/or ultraviolet irradiation treatment, surface heat treatment (high-frequency hardening, flame hardening, flame treatment, hot air treatment, etc.), anodizing treatment (alumite treatment, etc.), chemical conversion treatment (or chemical treatment) ), ion implantation, blasting (sand blasting, water blasting, etc.), etching (plasma treatment, electrolytic etching, chemical etching, etc.), solvent treatment, polishing, shot peening, plating [wet plating (electroplating, no Electroplating (chemical plating), etc.), dry plating (or vapor deposition) (PVD, CVD, etc.), hot-dip plating (hot-dip galvanizing, hot-dip aluminum plating, etc.)], painting, lining treatment (resin lining, glass lining, etc.), Thermal spraying treatment, primer treatment, and the like can be mentioned.

These surface treatments can be used alone or in combination of two or more. In the present invention, surface treatment (particularly, blasting treatment, etching treatment, corona discharge treatment, chromic acid treatment, ozone and/or ultraviolet irradiation treatment, surface heat treatment, chemical conversion treatment (or chemical treatment, primer treatment, etc.) is performed before bonding. In addition, since it can be adhered with high adhesive strength without performing surface modification and/or surface roughening treatment to improve adhesiveness, it is also excellent in simplicity (or productivity).

The form or shape of the substrate is not particularly limited, and examples thereof include one-dimensional shapes such as fibrous (thread-like, rope-like, wire-like, etc.); plate-like, sheet-like, film-like, foil-like, cloth-like or cloth-like. Two-dimensional shapes such as (woven fabric, knitted fabric, non-woven fabric, etc.), paper-like (fine paper, glassine paper, kraft paper, Japanese paper, etc.); three-dimensional shape such as a tubular shape, and the like.

These shapes may be used singly or may be a complex shape in which two or more types are combined. Usually, it often has a two-dimensional shape such as a plate shape or a film shape. When the resin material is in the form of a film, it may be an unstretched film or a uniaxially or biaxially stretched film (for example, a biaxially stretched film).

EXAMPLES The present invention will be described in more detail below based on examples, but the present invention is not limited by these examples. In addition, the preparation method of the used raw material is shown below.

[material]
(Adhesive raw material)
Polysilane: "OGSOL SI-10-40" manufactured by Osaka Gas Chemicals Co., Ltd., polymethylphenylsilane, number average molecular weight Mn 620, weight average molecular weight Mw 700
Tufselene: "Tafselene (registered trademark) X1102" manufactured by Sumitomo Chemical Co., Ltd., amorphous polypropylene resin Aurolen: "Auroren (registered trademark) 350S" manufactured by Nippon Paper Industries Co., Ltd., maleic anhydride-modified polypropylene resin, Melting point 65-75°C, amount of polar group medium (base material)
Aluminum plate material: Hikari Mall Co., Ltd. “Aluminum flat plate AP2 × 15”, width 15 mm, thickness 2 mm, flat plate of aluminum alloy A6063 with alumite finish, surface roughening treatment not performed Polypropylene film: ZAP Co., Ltd. (Zap) "OPP Roll", width 15 mm, thickness 100 μm.

[Comparative Example 1]
A coating liquid is prepared by dissolving 10 g of tough selenium in 90 g of toluene, and the coating liquid is dipped in an area 25 mm from the bottom (end in the length direction) of an aluminum plate and dried to a thickness of about 3 to 5 μm. A coating layer (adhesive layer) was prepared. A polypropylene film was adhered to this coating layer in the same width direction, and the coating layer portion was pressed at 160° C. for 80 seconds with a pressure of 0.1 MPa to prepare a fusion-bonded sample. The obtained sample was subjected to a 180° peel test (tensile speed: 50 mm/min, coating layer width during tensile test: 15 mm, N = 5) using a universal testing machine, and the average peel strength was 0.21 N. /15 mm. When the peeled surface of the sample after the test was checked, it was found to be peeled at the interface between the aluminum plate and the adhesive layer.

[Example 1]
A 180° peel test was conducted in the same manner as in Comparative Example 1 except that a coating solution prepared by mixing 90 g of toluene, 9.5 g of tafselene and 0.5 g of polysilane was used. was 15 mm. When the peeled surface of the sample after the test was checked, it was found to be peeled at the interface between the aluminum plate and the adhesive layer.

[Comparative Example 2]
A 180° peel test was conducted in the same manner as in Comparative Example 1 except that a coating solution prepared by mixing 90 g of toluene and 10 g of Aurorene was used. As a result, the average peel strength was 1.98 N/15 mm. When the peeled surface of the sample after the test was checked, peeling was found at both the interface between the aluminum plate and the adhesive layer and the interface between the polypropylene film and the adhesive layer.

[Example 2]
A 180° peel test was conducted in the same manner as in Comparative Example 1 except that a coating solution prepared by mixing 90 g of toluene, 9.5 g of Aurorene and 0.5 g of polysilane was used. /15 mm. When the peeled surface of the sample after the test was checked, peeling was found at both the interface between the aluminum plate and the adhesive layer and the interface between the polypropylene film and the adhesive layer.

[Comparative Example 3]
A sample was prepared in the same manner as in Comparative Example 1 except that the aluminum plate material and the polypropylene film were directly superimposed and pressed without forming a coating layer, and no adhesion was observed.

[Reference example 1]
A sample was prepared in the same manner as in Comparative Example 1 except that a coating solution prepared by mixing 90 g of toluene and 10 g of polysilane was used. , had almost no adhesion.

INDUSTRIAL APPLICABILITY The present invention can easily improve the adhesive strength not only between materials of the same type but also between materials of different types such as between a non-polar substrate and a polar substrate, and can be effectively used as an adhesive in particular.

Claims (10)

An adhesion improver for improving the adhesive strength of an adhesive containing a polyolefin resin and improving the adhesion between a resin material and an inorganic material,
Adhesion improver consisting of polysilane. Polysilane is represented by the following formulas (1a) and (1b)

(In the formula, R ¹ to R ³ each independently represent a hydrogen atom, a hydroxyl group, a halogen atom or an organic group.)
2. The adhesion improver according to claim 1, comprising at least one structural unit selected from the structural units represented by: 3. The adhesiveness improver according to claim 2, wherein one of ^R1 and ^R2 in formula (1a) is an alkyl group and the other is an aryl group. The adhesion improver according to any one of claims 1 to 3, wherein the polysilane has a weight average molecular weight Mw of 200 to 2,000. The adhesion improver according to any one of claims 1 to 4, wherein the resin material contains a polyolefin resin, and the inorganic material contains aluminum, an alloy thereof, or an oxide thereof. An adhesive comprising a polyolefin resin and the adhesion improver according to any one of claims 1 to 5 . 7. The adhesive according to claim 6 , wherein the polyolefin resin contained in the adhesive is a polypropylene resin. The adhesive according to claim 6 or 7 , wherein the polyolefin resin contained in the adhesive satisfies at least one of the following (i) to (ii).
(i) amorphous (ii) modified with at least one selected from acids or their anhydrides and epoxy compounds The adhesion according to any one of claims 6 to 8 , wherein the proportion of the adhesion improver is 0.5 to 10% by mass with respect to the total amount of the adhesion improver and the polyolefin resin contained in the adhesive. agent. A method of adding polysilane to improve the adhesive strength of an adhesive containing a polyolefin resin between a resin material and an inorganic material .