JP2018100315A - Resin composition for laser welding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition for laser welding which further reduces absorption in a visible light region (400-700 nm), is excellent in process properties as the application for laser welding and welding properties by irradiation with a laser beam, and is also excellent in a weld strength (hereinafter referred to as bond strength) of a welded body (hereinafter referred to as joined body) obtained by welding.SOLUTION: A resin composition for laser welding contains a salt-forming compound of squalirium [A] represented by general formula (1) and a resin [B] having a cationic group on the side chain, and a resin.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition for laser welding.

  A composition containing a specific phthalocyanine is known as a laser welding resin composition for joining thermoplastic resin molded members by local heating by laser light irradiation (Patent Document 1). However, since the phthalocyanine compound has an absorption called a soret band derived from a structure in the visible light region, particularly in the region of 400 to 500 nm, the transparency in the visible light region is not sufficient. Moreover, there are still problems in processability (uniform dispersibility, uniform coatability, process compatibility, etc.) as a laser welding application, and it has not yet been put into practical use.

JP, 2006-124964, A

  The present invention further reduces absorption in the visible light region (400 to 700 nm), is excellent in processability as a laser welding application, and weldability by laser light irradiation, and is a welded body obtained by welding (hereinafter, bonded) An object of the present invention is to provide a resin composition for laser welding excellent in welding strength (hereinafter also referred to as bonding strength).

The present invention includes a salt-forming compound of a squarylium [A] represented by the following general formula (1) and a resin [B] having a cationic group in a side chain, and a laser welding characterized by containing the resin The present invention relates to a resin composition.
General formula (1)

[In General Formula (1), X _{1 to} X ₁₀ each independently have a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a substituent. An aryl group which may have a substituent, an aralkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an amino group, a substituted amino group, —SO ₂ NR ₁ R ₂ , —COOR ₃ , —CONR ₄ R ₅ , a nitro group, a cyano group, or a halogen atom may be represented, and adjacent groups may form a ring. R _{1 to} R ₅ each independently represents a hydrogen atom or an alkyl group which may have a substituent. n represents an integer of 1 to 4. Z ⁺ represents a hydrogen ion or an inorganic or organic cation. ]

Moreover, this invention relates to the said laser welding resin composition whose resin [B] which has a cationic group in a side chain is a vinyl resin containing the structural unit represented by following General formula (2).
General formula (2)

[In General Formula (2), R ₆ represents a hydrogen atom or an alkyl group which may have a substituent. R _{7 to} R ₉ each independently represent a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an aryl group that may have a substituent; Two of _{7 to} R ₉ may be bonded to each other to form a ring. Q represents an alkylene group, an arylene group, —CONH—R ₁₀ — or —COO—R ₁₁ —, and R ₁₀ and R ₁₁ represent an alkylene group. Y ⁻ represents an inorganic or organic anion. ]

  Moreover, this invention relates to the said resin composition for laser welding whose n in General formula (1) is 1 or 2.

  The present invention also relates to the resin composition for laser welding, wherein the resin is a binder resin having a weight average molecular weight (Mw) of 10,000 to 100,000.

  The present invention also relates to a laser welding resin layer formed from the laser welding resin composition.

  The present invention also relates to the laser welding resin layer having an average transmittance in the visible light region of 80% or more.

  The present invention also relates to the laser welding resin layer having an absorption maximum in the near infrared region of 750 to 850 nm.

  The present invention also relates to a joined body in which a first joining member, the laser welding resin layer, and a second joining member are joined by laser welding.

  Moreover, this invention relates to the manufacturing method of the conjugate | zygote which joins a 1st joining member, the said laser welding resin layer, and a 2nd joining member by irradiating a laser beam.

  Furthermore, this invention forms a laser welding resin layer as described in any one of Claims 5-7 on a 1st joining member, Then, it bonds with a 2nd joining member and irradiates a laser beam. The present invention relates to a method for manufacturing a joined body to be joined.

  The laser welding resin composition of the present invention further reduces absorption in the visible light region (400 to 700 nm), is excellent in processability as a laser welding application, and weldability by laser light irradiation, and is obtained by the welding. The welded body has a high visible light transmittance and excellent weld strength.

<Squarylium [A]>
The squarylium [A] represented by the general formula (1) of the present invention will be described in detail.

General formula (1)

[In General Formula (1), X _{1 to} X ₁₀ each independently have a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a substituent. An aryl group which may have a substituent, an aralkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an amino group, a substituted amino group, —SO ₂ NR ₁ R ₂ , —COOR ₃ , —CONR ₄ R ₅ , a nitro group, a cyano group, or a halogen atom may be represented, and adjacent groups may form a ring. R _{1 to} R ₅ each independently represents a hydrogen atom or an alkyl group which may have a substituent. n represents an integer of 1 to 4. Z ⁺ represents a hydrogen ion or an inorganic or organic cation. ]

Examples of the “alkyl group which may have a substituent” in X _{1 to} X ₁₀ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, a tert-amyl group, a 2-ethylhexyl group, Stearyl group, chloromethyl group, trichloromethyl group, trifluoromethyl group, 2-methoxyethyl group, 2-chloroethyl group, 2-nitroethyl group, cyclopentyl group, cyclohexyl group, dimethylcyclohexyl group, etc. Of these, a methyl group, an ethyl group, and an n-propyl group are preferable from the viewpoint of difficulty in synthesis and reduction of absorption in the visible light region, and a methyl group is particularly preferable.

As the “alkenyl group which may have a substituent” in X _{1 to} X ₁₀ , a vinyl group, 1-propenyl group, allyl group, 2-butenyl group, 3-butenyl group, isopropenyl group, isobutenyl group, 1 -Pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, etc. Among these, a vinyl group and an allyl group are preferable from the viewpoints of synthesis difficulty and reduced absorption in the visible light region.

In X _{1 to} X ₁₀ , as the “aryl group optionally having substituent (s)”, phenyl group, naphthyl group, 4-methylphenyl group, 3,5-dimethylphenyl group, pentafluorophenyl group, 4-bromophenyl Group, 2-methoxyphenyl group, 4-diethylaminophenyl group, 3-nitrophenyl group, 4-cyanophenyl group, etc. Among them, phenyl group, 4-methylphenyl group are the synthesis difficulty level, and This is preferable from the viewpoint of reducing absorption in the visible light region.

Examples of the “aralkyl group which may have a substituent” in X _{1 to} X ₁₀ include a benzyl group, a phenethyl group, a phenylpropyl group, and a naphthylmethyl group. Among these, a benzyl group is difficult to synthesize. And from the viewpoint of reducing absorption in the visible light region.

In X _{1 to} X ₁₀ , the “alkoxy group having a substituent” includes a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an n-octyloxy group, and 2-ethylhexyloxy. Group, trifluoromethoxy group, cyclohexyloxy group, stearyloxy group, etc. Among them, methoxy group, ethoxy group, trifluoromethoxy group are preferred in terms of synthesis difficulty and reduction of absorption in the visible light region. preferable.

As the “aryloxy group which may have a substituent” in X _{1 to} X ₁₀ , phenoxy group, naphthyloxy group, 4-methylphenyloxy group, 3,5-chlorophenyloxy group, 4-chloro-2- Examples thereof include methylphenyloxy group, 4-tert-butylphenyloxy group, 4-methoxyphenyloxy group, 4-diethylaminophenyloxy group, 4-nitrophenyloxy group, and among these, phenoxy group, naphthyloxy group Is preferable from the viewpoints of synthesis difficulty and reduction of absorption in the visible light region.

As the “substituted amino group” in X _{1 to} X ₁₀ , the methylamino group, ethylamino group, isopropylamino group, n-butylamino group, cyclohexylamino group, stearylamino group, dimethylamino group, diethylamino group, dibutylamino group N, N-di (2-hydroxyethyl) amino group, phenylamino group, naphthylamino group, 4-tert-butylphenylamino group, diphenylamino group, N-phenyl-N-ethylamino group, and the like. Among these, a dimethylamino group and a diethylamino group are preferable from the viewpoints of synthesis difficulty and reduction of absorption in the visible light region.

Examples of the “halogen atom” in X _{1 to} X ₁₀ include fluorine, bromine, chlorine, and iodine.

In X _{1 to} X ₁₀ , adjacent groups may form a ring, and examples thereof include the following structures, but are not limited thereto.

In R _{1 to} R ₅ , the “alkyl group optionally having substituent (s)” has the same meaning as X _{1 to} X ₁₀ .

X _{1 to} X ₁₀ preferably contain an unsubstituted alkyl group from the viewpoints of synthesis difficulty, uniform dispersibility, uniform coatability, and absorption reduction in the visible light region, and X ₃ , X ₄ , X ₇ It is more preferable that at least one of X ₈ and X ₈ is an unsubstituted alkyl group, and it is particularly preferable that X ₃ and X ₇ are unsubstituted alkyl groups. The unsubstituted alkyl group is preferably a methyl group.

As the “inorganic or organic cation” of Z ⁺ , known ones can be used without limitation, and specific examples include metal atoms, ammonium compounds, pyridinium compounds, imidazolium compounds, phosphonium compounds, sulfonium compounds and the like. it can. As Z ⁺ , a hydrogen atom, a metal atom, or an ammonium compound is preferable from the viewpoints of synthesis difficulty and reduction of absorption in the visible light region.

  N in the general formula (1) is preferably 1 or 2 from the viewpoint of the difficulty of synthesis and the absorption reduction in the visible light region, and particularly preferably n = 2.

<Method for producing squarylium [A]>
Although the following method can be considered as a manufacturing method of squarylium [A], squarylium [A] used for this invention is not limited by this following manufacturing method. The 1,8-diaminonaphthalene represented by the following formula (3) and the cyclohexanone represented by the following general formula (4) were condensed with heating in a solvent together with a catalyst, and then the following formula (5) was obtained. The indicated 3,4-dihydroxy-3-cyclobutene-1,2-dione is added and further heated to reflux for condensation to obtain a squarylium [A] precursor represented by the general formula (6). Furthermore, squarylium [A] (Z ⁺ = hydrogen ion) represented by the general formula (7) can be obtained by sulfonating the squarylium [A] precursor in an appropriate concentration of sulfuric acid. The general formula (7) squarylium indicated [A] (Z + ⁼ hydrogen ion) to be to any ionic compound and salt exchange reaction, to convert Z ⁺ to any inorganic or organic cation it can.

<Resin having cationic group in side chain [B]>
The resin [B] having a cationic group in the side chain represented by the general formula (2) of the present invention will be described in detail.

General formula (2)

[In General Formula (2), R ₆ represents a hydrogen atom or an alkyl group which may have a substituent. R _{7 to} R ₉ each independently represent a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an aryl group that may have a substituent; Two of _{7 to} R ₉ may be bonded to each other to form a ring. Q represents an alkylene group, an arylene group, —CONH—R ₁₀ — or —COO—R ₁₁ —, and R ₁₀ and R ₁₁ represent an alkylene group. Y ⁻ represents an inorganic or organic anion. ]

Examples of the “alkyl group which may have a substituent” in R ₆ include a methyl group, an ethyl group, a propyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-hexyl group, and a cyclohexyl group. Can be mentioned. As this alkyl group, a C1-C12 alkyl group is preferable, a C1-C8 alkyl group is more preferable, and a C1-C4 alkyl group is especially preferable.

When the alkyl group represented by R ₆ has a substituent, examples of the substituent include a hydroxyl group and an alkoxyl group. Among the above, R ₆ is most preferably a hydrogen atom or a methyl group.

As the “alkyl group optionally having substituent (s)” in R _{7 to} R ₉ , a linear alkyl group (methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, etc.), branched alkyl groups (isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, 2-ethylhexyl and 1, 1,3,3-tetramethylbutyl, etc.), cycloalkyl groups (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.) and bridged cyclic alkyl groups (norbornyl, adamantyl, pinanyl, etc.). As this alkyl group, a C1-C18 alkyl group is preferable, More preferably, it is a C1-C8 alkyl group.

In R _{7 to} R ₉ , the “optionally substituted alkenyl group” may be a linear or branched alkenyl group (vinyl, allyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3 -Butenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, etc.), cycloalkenyl groups (2-cyclohexenyl and 3- Cyclohexenyl etc.). As this alkenyl group, a C2-C18 alkenyl group is preferable, More preferably, it is a C2-C8 alkenyl group.

Examples of the “aryl group optionally having substituent (s)” in R _{7 to} R ₉ include a monocyclic aryl group (phenyl and the like), a condensed polycyclic aryl group (naphthyl, anthracenyl, phenanthrenyl, anthraquinolyl, fluorenyl, naphthoquinolyl, etc. ) And an aromatic heterocyclic hydrocarbon group (thienyl (a group derived from thiophene), furyl (a group derived from furan), pyranyl (a group derived from pyran), pyridyl (a group derived from pyridine), 9-oxoxanthenyl (group derived from xanthone), 9-oxothioxanthenyl (group derived from thioxanthone) and the like.

When the alkyl group, alkenyl group and aryl group represented by R _{7 to} R ₉ have a substituent, examples of the substituent include a halogen atom, a hydroxyl group, an alkoxyl group, an aryloxy group, an alkenyl group, an acyl group, Examples include a substituent selected from an alkoxycarbonyl group, a carboxyl group, a phenyl group, and the like. Among these substituents, a halogen atom, a hydroxyl group, an alkoxyl group, and a phenyl group are particularly preferable.

As R < ₇ > -R < ₉ >, the alkyl group which may have a substituent is preferable, and an unsubstituted alkyl group is still more preferable. Two of R _{7 to} R ₉ may be bonded to each other to form a ring.

In the general formula (2), components of the Q connecting the acrylic sites and ammonium base is an alkylene group, an arylene _{group, -CONH-R 10 -, -} COO-R 11 - _{represents, R 10} and _{R 11} represents an alkylene group Among them, -CONH-R ₁₀ -and -COO-R ₁₁ -are preferable because of polymerizability and availability. Examples of the “alkylene group” in R ₁₀ and R ₁₁ include a methylene group, an ethylene group, a propylene group, and a butylene group, and among these, an ethylene group is particularly preferable.

The component of Y ⁻ in the general formula (2) constituting the counter anion of the resin [B] may be an inorganic or organic anion. As the counter anion, known ones can be used without limitation. Specifically, hydroxide ions; halogen ions such as chloride ions, bromide ions, and iodide ions; carboxylate ions such as formate ions and acetate ions; Carbonate ions, bicarbonate ions, nitrate ions, sulfate ions, sulfite ions, chromate ions, dichromate ions, phosphate ions, cyanide ions, permanganate ions, and even hexacyanoferrate (III) ions And complex ions. From the viewpoint of synthesis suitability and stability, halogen ions and carboxylate ions are preferable, and halogen ions are most preferable. When the counter anion is an organic acid ion such as a carboxylate ion, the organic acid ion may be covalently bonded in the resin to form an inner salt.

  In order to obtain a vinyl resin containing a structural unit represented by the general formula (2) which is a preferred embodiment of the present invention, only a method of copolymerizing an ethylenically unsaturated monomer having an ammonium base as a monomer component is used. Alternatively, after obtaining a vinyl resin having an amino group obtained by copolymerizing an ethylenically unsaturated monomer having an amino group as a monomer component, it may be obtained by a method in which an onium chlorinating agent is reacted and ammonium salified. good.

  Below, the specific example of the ethylenically unsaturated monomer which can be used in order to obtain the vinyl resin containing the structural unit represented by General formula (2) which is a preferable aspect of this invention is shown. In addition, in this specification, when showing either or both of "acryl, methacryl", it may describe as "(meth) acryl". Similarly, when one or both of “acryloyl and methacryloyl” are indicated, it may be described as “(meth) acryloyl”.

  Examples of the ethylenically unsaturated monomer having a quaternary ammonium base include (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyltriethylammonium chloride, (meth) acryloyloxyethyldimethylbenzylammonium chloride, (meta ) Alkyl (meth) acrylate quaternary ammonium salts such as acryloyloxyethylmethylmorpholino ammonium chloride, (meth) acryloylaminopropyltrimethylammonium chloride, (meth) acryloylaminoethyltriethylammonium chloride, (meth) acryloylaminoethyldimethylbenzyl Alkyl (meth) acryloylamide quaternary ammonium salts such as ammonium chloride, dimethyl Luzia Lil ammonium methyl sulfate, trimethyl vinyl phenyl ammonium chloride.

  Examples of the ethylenically unsaturated monomer having an amino group include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dipropylaminoethyl (meth) acrylate, diisopropylaminoethyl (meth) acrylate, and dibutylamino. Ethyl (meth) acrylate, diisobutylaminoethyl (meth) acrylate, di-t-butylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, dipropylaminopropyl (meth) acrylamide, diisopropyl Aminopropyl (meth) acrylamide, dibutylaminopropyl (meth) acrylamide, diisobutylaminopropyl (meth) acrylamide, di-t-butyl Examples include (meth) acrylic acid esters having a dialkylamino group such as minopropyl (meth) acrylamide or (meth) acrylamide, and styrenes having a dialkylamino group such as dimethylaminostyrene and dimethylaminomethylstyrene, diallylmethylamine, diallylamine And amino group-containing aromatic vinyl monomers such as N-vinylpyrrolidine, N-vinylpyrrolidone and N-vinylcarbazole.

  Examples of the onium chloride agent include alkyl sulfates such as dimethyl sulfate, diethyl sulfate, or dipropyl sulfate, sulfonate esters such as methyl p-toluenesulfonate, or methyl benzenesulfonate, methyl chloride, ethyl chloride, propyl chloride, or Examples thereof include alkyl chlorides such as octyl chloride, alkyl bromides such as methyl bromide, ethyl bromide, propyl bromide, and octyl chlorobromide, benzyl chloride, and benzyl bromide.

  The reaction between the ethylenically unsaturated monomer having an amino group and the onium chlorinating agent is usually performed by dropping an equimolar amount or less of the onium chlorinating agent into the amino group-containing ethylenically unsaturated monomer solution. Can be done. The temperature during the ammonium chlorination reaction is about 90 ° C. or less, and particularly when the vinyl monomer is ammonium chlorinated, it is preferably about 30 ° C. or less, and the reaction time is about 1 to 4 hours.

Alternatively, an alkoxycarbonylalkyl halide can also be used as the onium chlorinating agent. The alkoxycarbonylalkyl halide is represented by the following general formula (8).
_D-R 12 -COOR ₁₃ formula (8)
(In General Formula (8), D is a halogen such as chlorine or bromine, preferably bromine, and R ₁₂ is an alkylene group having 1 to 6 carbon atoms, preferably 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms. And R ₁₃ is a lower alkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms.)

Reaction of the ethylenically unsaturated monomer and alkoxycarbonylalkyl halide with an amino group, after equimolar following alkoxycarbonylalkyl halide was reacted in the same manner as in the above onium chloride agent to an amino group, a -COOR ₁₃ It is obtained by hydrolysis and conversion to carboxylate ions (—COO—). Thereby, the ethylenically unsaturated monomer which has a carboxybetaine structure shown by General formula (8) Formula, and has an ammonium base can be obtained.

  Other examples of the ethylenically unsaturated monomer that can be used other than the structural unit represented by the general formula (2) include (meth) acrylic acid esters, crotonic acid esters, vinyl esters, and maleic acid. Diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamides, vinyl ethers, vinyl alcohol esters, styrenes, (meth) acrylonitrile and the like are preferable.

  Specific examples of such vinyl monomers include the following compounds.

  Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, (meth) acrylic acid 2- Ethylhexyl, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-Methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, (meth) acrylic acid Diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene glycol monoethyl ether, ( Β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclo (meth) acrylate Pentenyloxyethyl, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromophenyl (meth) acrylate And (meth) acrylic acid tribromophenyloxyethyl.

  Examples of crotonic acid esters include butyl crotonate and hexyl crotonate.

  Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like. Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.

  Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.

  Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

Examples of (meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn -Butyl acryl (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N , N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide and the like.

  Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether. Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethyl Examples thereof include styrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, and α-methylstyrene.

  In addition, the ethylenically unsaturated monomer that can be used other than the structural unit represented by the general formula (2) may further include a copolymer unit derived from a monomer having an acid group.

  As monomers having an acid group, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid; maleic acid, maleic anhydride, fumaric acid, itaconic acid, anhydrous Unsaturated dicarboxylic acids such as itaconic acid, citraconic acid, citraconic anhydride and mesaconic acid or their anhydrides; trivalent or higher unsaturated polycarboxylic acids or their anhydrides; succinic acid mono (2-acryloyloxyethyl) ), Succinic acid mono (2-methacryloyloxyethyl), phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl) monovalent polyvalent carboxylic acid mono [ (Meth) acryloyloxyalkyl] esters; ω-carboxy-polycaprolactone monoacrylate, ω-carboxy-polycaprolacto Include mono (meth) acrylates such as both terminal carboxy polymers such monomethacrylate.

  Examples of a method for obtaining a vinyl resin containing the structural unit represented by the general formula (2) suitable for the present invention include anionic polymerization, living anionic polymerization, cationic polymerization, living cationic polymerization, free radical polymerization, and living radical polymerization. Any known method can be used. Of these, free radical polymerization or living radical polymerization is preferred.

In the case of the free radical polymerization method, it is preferable to use a polymerization initiator. As the polymerization initiator, for example, an azo compound and an organic peroxide can be used. Examples of the azo compounds include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2 , 2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate) 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), or 2,2′-azobis [2- (2-imidazolin-2-yl ) Propane] and the like. Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxy Examples thereof include dicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, and diacetyl peroxide. These polymerization initiators can be used alone or in combination of two or more. The reaction temperature is preferably 40 to 150 ° C., more preferably 50 to 110 ° C., and the reaction time is preferably 3 to 30 hours, more preferably 5 to 20 hours.

  In the living radical polymerization method, side reactions that occur in general radical polymerization are suppressed, and further, since the growth of polymerization occurs uniformly, it is possible to easily synthesize block polymers and resins with uniform molecular weight.

Among them, the atom transfer radical polymerization method using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst is applicable to a wide range of monomers, and has a polymerization temperature applicable to existing equipment. It is preferable in that it can be adopted. An atom transfer radical polymerization method can be performed by the method described in the following references 5-12.
(Reference 5) Fukuda et al., Prog. Polym. Sci. 2004, 29, 329
(Reference 6) Matyjaszewski et al., Chem. Rev. 2001, 101, 2921
(Reference 7) Matyjaszewski et al. Am. Chem. Soc. 1995, 117, 5614
(Reference 8) Macromolecules 1995, 28, 7901, Science, 1996, 272, 866
(Reference 9) Pamphlet of International Publication No. 96/030421 (Reference 10) Pamphlet of International Publication No. 97/018247 (Reference 11) JP-A-9-208616 (Reference 12) JP-A-8-411117

  It is preferable to use an organic solvent for the polymerization. The organic solvent is not particularly limited, but for example, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether Acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, or the like is used. Two or more kinds of these polymerization solvents may be mixed and used.

  The amount of the ammonium base present in the vinyl-based resin containing the structural unit represented by the general formula (2) suitable for the present invention is not particularly limited, but the ammonium salt value of the resin is 10 to 200 mgKOH / It is preferable that it is g, and it is more preferable that it is 20-130 mgKOH / g.

  In order for the ammonium salt value of the resin to satisfy the above range, the preferred content of the structural unit having a quaternary ammonium base is 4 to 74% by weight in a total of 100% by weight of the structural units constituting the resin, A more preferred range is 8 to 48% by weight.

  Although the molecular weight of the vinyl resin containing the structural unit represented by the general formula (2) used in the present invention is not particularly limited, the converted weight average molecular weight measured by gel permeation chromatography (GPC). Is preferably 1,000 to 500,000, and more preferably 3,000 to 15,000.

  In the resin [B] having a cationic group in the side chain, the total content of the structural unit represented by the general formula (2) is not particularly limited, but the resin [B] having a cationic group in the side chain. From the viewpoint of solvent solubility and coloring power of the salt-forming compound, the total content of the structural unit represented by the general formula (2) is 5% by weight, assuming that the total structural unit contained in 100% by mass. % Or more, and more preferably 10 to 50% by mass.

<Method for producing salt-forming compound>
The salt-forming compound of the present invention is prepared by stirring or vibrating an aqueous solution in which squarylium [A] and a resin [B] having a cationic group are dissolved in the side chain, or cation in the aqueous solution and side chain of squarylium [A]. It can be easily obtained by mixing an aqueous solution of the resin [B] having a functional group with stirring or vibration. In the aqueous solution, the anionic group of squarylium [A] and the cationic group of resin [B] are ionized and these are ionically bonded, and the ion-bonded portion becomes water-insoluble and precipitates. On the contrary, a salt composed of a counter cation of squarylium [A] and a counter anion of resin [B] is water-soluble and can be removed by washing or the like. The squarylium [A] and the resin [B] having a cationic group in the side chain may be used alone or in a plurality of types having different structures.

  In order to dissolve squarylium [A] and the resin [B] having a cationic group in the side chain as an aqueous solution used at the time of salt formation, a mixed solution of water and a water-soluble organic solvent may be used. Examples of the water-soluble organic solvent include methanol, ethanol, n-propanol, isopropanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, n-butanol, isobutanol, 2- (methoxymethoxy) ethanol, 2- Butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene Glycol, propylene glycolic monomethyl ether acetate, dipropylene glycol, dipropylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol, triethylene glycol monomethyl ether, polyethylene glycol, glycerin, tetraethylene glycol, dipropylene glycol, acetone, diacetone alcohol, aniline, pyridine, ethyl acetate, isopropyl acetate, methyl ethyl ketone , N, N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran (THF), dioxane, 2-pyrrolidone, 2-methylpyrrolidone, N-methyl-2-pyrrolidone, 1,2-hexanediol, 2,4,6-hexanetriol , Tetrafurfuryl alcohol, 4-methoxy-4-methylpentanone and the like. These water-soluble organic solvents are preferably used in an amount of 5 to 50% by weight, and most preferably 5 to 20% by weight, based on the total weight of the aqueous solution (100% by weight).

  The ratio of the squarylium [A] and the resin [B] having a cationic group in the side chain is such that the molar ratio of the total cation unit of the resin [B] to the total anionic group of the squarylium [A] is 10/1. If it is in the range of 1/10, the salt-forming compound of the present invention can be suitably adjusted, preferably in the range of 4/1 to 1/4, and particularly preferably in the range of 2/1 to 1/2.

When n in the squarylium [A] represented by the general formula (1) is 2 or more, all sulfo groups may form a salt with the resin [B], or one or more sulfo groups may form the resin [B]. And the remaining sulfo group counter cation may remain in the Z ⁺ state. By changing the molar ratio in the production, the ratio of the resin [B] and Z ⁺ can be controlled.

<Laser welding resin composition>
The laser welding resin composition of the present invention will be described in detail.
The resin composition for laser welding of the present invention is a resin composition containing a salt-forming compound and a resin. As the resin, conventionally known ones can be used, and two or more kinds may be used in combination, as described later. A thermoplastic resin may be sufficient and resin which does not have thermoplasticity may be sufficient. Moreover, as a method of using the laser welding resin composition, it is desired to provide a layer formed from the laser welding resin composition between those to be bonded and to bond via the laser welding resin composition layer. Objects may be welded together (Method 1), and a layer formed from a laser welding resin composition using a thermoplastic resin as a resin and a material to be joined are bonded together to form a laser welding resin layer Although what you want to join may be welded (method 2), it is not limited to these.
Below, the resin composition suitable for the said methods 1 and 2 is demonstrated, respectively.

[Laser welding resin composition suitable for method 1]
In the case of the above-mentioned method 1, the laser welding resin composition can be applied, applied, and printed by a conventionally known method at a position where the joining member is desired to be joined, and a binder resin is preferably used as the resin.

(Binder resin)
As the binder resin, any known one can be used without limitation as long as it can be coated on the joining member, and it may or may not be a thermoplastic resin. From the viewpoint of invisibility, the resin preferably has a spectral transmittance of 80% or more, more preferably 95% or more in the entire wavelength region of the visible light region (400 to 700 nm).

  The weight average molecular weight (Mw) of the binder resin is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.

  These binder resins can be used alone or in combination of two or more at any ratio as required. The binder resin is preferably used in an amount of 30 parts by weight or more with respect to the total weight of 100 parts by weight of the salt-forming compound because the film forming property is good. It is preferable to use it in an amount of less than parts.

(Salt making compound)
In the resin composition for laser welding, the salt-forming compound may be used in either a dispersed state or a dissolved state, and the salt-forming compound is used alone or in combination of two or more at any ratio as necessary. be able to. Moreover, although the salt-forming compound in the laser welding resin composition can be adjusted as necessary, it is preferably contained in the laser welding resin composition in an amount of 0.01 to 50% by mass, More preferably, 30% by mass is contained.

  The laser welding resin composition may contain a dispersant, an organic solvent, and other components in addition to the salt-forming compound and the resin.

(Dispersant)
Any known dispersant can be used without limitation as long as it can disperse the salt-forming compound of the present invention. A low molecular type dispersant such as an activator can also be used, and a high molecular type dispersant such as a resin type dispersant can also be used. In addition, as an adsorbing group in the dispersant, basic groups such as acidic groups such as carboxylic acid group, sulfonic acid group, and phosphoric acid group, primary amino group, secondary amino group, tertiary amino group, and quaternary ammonium salt are used. Examples thereof include neutral groups such as a hydroxyl group and a hydroxyl group, but can be used without any particular limitation. These dispersants can be used alone or in combination of two or more at any ratio as required. These dispersants are preferably 5 to 200% by weight based on the total amount of the salt-forming compound in the laser welding resin composition (100% by weight), and 10 to 150% by weight from the viewpoint of processability. More preferably.

(Organic solvent)
Any known organic solvent can be used as long as it can dissolve or disperse the salt-forming compound of the present invention. These organic solvents can be used individually by 1 type or in mixture of 2 or more types. Moreover, since the organic solvent can adjust the resin composition for laser welding to an appropriate viscosity and can form a coating film having a desired uniform film thickness, it is 500 to 4000 with respect to 100 parts by weight of the total weight of the salt-forming compound. It is preferably used in an amount of parts by weight.

(Other ingredients)
The laser welding resin composition is a composition containing a salt-forming compound, but contains any component other than the salt-forming compound and the resin, depending on the composition and process, as long as the effects of the present invention are not impaired. You may go out. As optional components, near-infrared absorbing dyes other than the salt-forming compound of the present invention, curing agent, curing accelerator, crosslinking agent, photopolymerizable monomer, oligomer, sensitizer, polymerization initiator, flow regulator, You may contain various additives, such as a leveling agent and antioxidant.

(Production method)
The resin composition for laser welding can be produced by any method, and an example thereof will be described below. When the salt-forming compound is used by “dissolving”, in addition to the salt-forming compound and the resin, an organic solvent capable of dissolving the salt-forming compound, other components, etc. are added and dissolved using a known dissolution means. The resin composition for laser welding in a state can be produced. Known dissolution means include, but are not limited to, stirring, heating, sonication and the like. When the salt-forming compound is “dispersed” and used, in addition to the salt-forming compound and the resin, a dispersing agent capable of dispersing the salt-forming compound, an organic solvent, other components, and the like are added, and a known dispersion means is used. Thus, a dispersed resin composition for laser welding can be produced. Known dispersing means include, but are not limited to, a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor.

(Joining member)
The joining member that may be coated with the laser welding resin composition of the present invention is preferably a moldable member, and the following thermoplastic resins are suitably used. For example, acrylic resin, polycarbonate resin, polystyrene resin, low density polyethylene resin, polypropylene resin, polyurethane resin, polyamide resin, polyacetal resin, polyphenylene sulfide resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polycycloolefin resin, polysulfone resin, poly Examples include ether sulfone resins and fluororesins. The molded member is preferably a thermoplastic resin having high transmittance in the visible light region (400 to 700 nm) and high transparency. The thermoplastic resin has a light transmittance in the visible light region of 80% or more, and more preferably 90% or more. However, when the resin contained in the resin composition for laser welding is a thermoplastic resin, the joining member does not need to be a thermoplastic resin, and a conventionally known molded member can be used.

(Coating method)
The resin composition for laser welding can be used after being applied to a location where the molded member is desired to be joined. As a coating method, a known method can be used without limitation. Examples of the coating method include, but are not limited to, printing methods such as spray coating, spin coating, slit coating, roll coating, ink jet, screen, and gravure.

(Transparency of coated joint member)
As the bonding member coated with the laser welding resin composition by the above method, one having a visible light transmittance of 80% or more can be obtained. Preferably it is 85% or more, More preferably, it is 90% or more. Under the present circumstances, the joining member which coated the resin composition for laser welding has an absorption maximum in the near infrared region of 750-850 nm, and the near-infrared transmittance of 808 nm is in the range of 50 ± 5%. By changing the concentration of the resin composition for laser welding and the film thickness of the coating film, the transmittance in the near-infrared region and visible light region can be controlled, and it can be used for various laser strengths and welding applications. be able to. For example, by adjusting the coating film so that the near-infrared transmittance at 808 nm is higher than 50%, the visible light transmittance is further improved, and the transparency of the joining member itself can be approached as much as possible. It can be suitably used in applications that require design properties.

[Laser welding resin composition suitable for method 2]
In the case of the above method 2, the resin is preferably a thermoplastic resin, and it is preferable to knead a salt-forming compound into the thermoplastic resin to obtain a laser-welded resin composition.

(Thermoplastic resin)
The thermoplastic resin is not particularly limited. For example, acrylic resin, polycarbonate resin, polystyrene resin, low density polyethylene resin, polypropylene resin, polyurethane resin, polyamide resin, polyacetal resin, polyphenylene sulfide resin, polyethylene terephthalate resin, polybutylene terephthalate. Examples thereof include resins, polycycloolefin resins, polysulfone resins, polyether sulfone resins, and fluorine resins. These thermoplastic resins may be used individually by 1 type, or may use 2 or more types together.

  The acrylic resin is not particularly limited, and examples thereof include alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate; polymers such as methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate; A copolymer obtained from vinyl acetate, vinyl chloride, styrene, acrylonitrile, methacrylonitrile, or the like is used as the main raw material and at least one selected from the group consisting of acrylates and alkyl methacrylates. Further, the weights described in Japanese Patent Publication No. 59-36646, Japanese Patent Publication No. 62-19309, Japanese Patent Publication No. 63-20459, Japanese Patent Publication No. 63-77963, Japanese Patent Publication No. 2006-146029, and the like. Coalescence can be used. Among them, for example, a copolymer obtained by using 50 to 99.95 mol% of methyl methacrylate and 0.05 to 50 mol% of another copolymerizable monomer such as alkyl acrylate is preferable. These can be used alone or in combination.

  The polystyrene resin is not particularly limited. For example, styrene monomer (for example, styrene, methylstyrene, ethylstyrene, isopropylstyrene, dimethylstyrene, paramethylstyrene, chlorostyrene, bromostyrene, vinyltoluene, vinylxylene) Homopolymer), copolymer of styrene and other monomers (for example, styrene monomer and acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, methyl methacrylate, maleic anhydride, butadiene And the like). Among them, polystyrene, acrylonitrile-styrene copolymer, methyl methacrylate-styrene copolymer, acrylonitrile-methyl methacrylate-styrene copolymer, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-acrylic rubber-styrene resin, acrylonitrile. -It is preferable to use EPDM-styrene resin or the like. These polystyrene resins may be used alone or in combination of two or more.

  The low density polyethylene resin is not particularly limited, and examples thereof include a high pressure method low density polyethylene resin, a linear low density polyethylene resin, and a low density ethylene-α-olefin copolymer. These low density polyethylene resins may be used alone or in combination of two or more.

  The polypropylene resin is not particularly limited. For example, a propylene homopolymer (homopolypropylene), a propylene random copolymer (for example, propylene / ethylene random) with other olefin components containing 70% by weight or more of a propylene component in addition to homopolypropylene. Copolymer), propylene block copolymer (such as propylene / ethylene random copolymer) and the like. These polypropylene resins may be used alone or in combination of two or more.

  The polyurethane resin is not particularly limited, and examples thereof include conventionally known polyurethane resins having a urethane bond (—NHCOO—), a urea bond, a burette bond, and an allophanate bond in the molecule. These polyurethane resins may be used alone or in combination of two or more.

  There is no limitation in particular as a polyamide resin, A well-known polyamide resin can be used. For example, polyamide 66, polyamide 46, polyamide 610, polyamide 612, polyamide 6T (6T is a polyamide polymer composed of hexamethylenediamine and terephthalic acid), polyamide 6I (6I is obtained by condensation polymerization of diamine and dicarboxylic acid, Polyamide polymer consisting of hexamethylenediamine and isophthalic acid), polyamide MXD6 (MXD6 is a polyamide polymer consisting of metaxylylenediamine and adipic acid), polyamide 9T (9T is a polyamide polymer consisting of nonanediamine and terephthalic acid), At least one homopolymer selected from the group consisting of polyamide 6, polyamide 12 obtained by ring-opening polymerization of lactam, and polyamide 11 obtained by self-polycondensation of ω-aminocarboxylic acid, and / or copolymers thereof Young Blend, and the like. These polyamide resins may be used alone or in combination of two or more.

  The polyacetal resin is not particularly limited, and examples thereof include a polyacetal homopolymer, a copolymer of formaldehyde and trioxane, and the like. These polyacetal resins may be used alone or in combination of two or more.

  The polyphenylene sulfide resin is not particularly limited. For example, a polymer having a p-phenylene sulfide unit as a basic repeating unit, an m-phenylene sulfide unit, an o-phenylene sulfide unit, p, p'-diphenylene ketone-sulfide unit, p, p'-diphenylenesulfone-sulfide unit, p, p'-biphenylene-sulfide unit, p, p'-diphenylene ether-sulfide unit, p, p'-di Examples thereof include copolymers containing repeating units such as phenylenemethylene-sulfide units, p, p'-diphenylenecumenyl-sulfide units, and various naphthyl-sulfide units. These polyphenylene sulfide resins may be used alone or in combination of two or more.

  The polyethylene terephthalate resin is not particularly limited, for example, a homopolymer of polyethylene terephthalate; a part of the structural unit of the polyethylene terephthalate polymer structure, for example, a part of the terephthalic acid unit replaced with an isophthalic acid unit And polyethylene terephthalate-based resins. Moreover, what added polyethylene naphthalate etc. further to such a polyethylene terephthalate-type resin may be used. These polyethylene terephthalate resins may be used alone or in combination of two or more.

  The polybutylene terephthalate resin is not particularly limited. For example, a polybutylene terephthalate homopolymer composed of terephthalic acid and 1,4-butanediol, and naphthalenedicarboxylic acid, diethylene glycol, 1,4- Examples thereof include a copolymer obtained by copolymerizing cyclohexane dimethanol. These polybutylene terephthalate resins may be used alone or in combination of two or more.

  The polycycloolefin (COP) resin is not particularly limited, and examples thereof include a polymer of norbornene; a copolymer of norbornene and an olefin; and a polymer of unsaturated alicyclic hydrocarbon such as cyclopentadiene. These polycycloolefin resins may be used alone or in combination of two or more.

The polysulfone resin is not particularly limited as long as it has a molecular structure including a plurality of sulfonyl groups (—SO ₂ —). For example, a polyethersulfone resin containing a plurality of ether bonds (—O—) in the molecule in addition to the sulfonyl group; a polyphenylsulfone resin containing a plurality of aromatic hydrocarbons in the molecule in addition to the sulfonyl group; other than the sulfonyl group Furthermore, a polyether polyphenyl sulfone resin containing a plurality of ether bonds and a plurality of aromatic hydrocarbons in the molecule can be mentioned. These polyphenylene sulfide resins may be used alone or in combination of two or more.

  The fluororesin is not particularly limited, and for example, polyfluorinated ethylene, polydifluorinated ethylene, polytetrafluoroethylene, ethylene-2 fluoroethylene copolymer, ethylene-4 fluoroethylene copolymer, 4 fluoroethylene copolymer. Ethylene-perfluoroalkoxyethylene copolymer and the like. These fluororesins may be used alone or in combination of two or more.

  As the thermoplastic resin, a thermoplastic resin having high transparency in the visible light region (400 to 700 nm) and high transparency is preferable. The thermoplastic resin has a light transmittance in the visible light region of 80% or more, and more preferably 90% or more.

More preferable examples of the thermoplastic resin include polystyrene resin, polymethyl methacrylate, cycloolefin polymer, polycarbonate, and polyethylene terephthalate resin.

(Salt making compound)
In the resin composition for laser welding, the salt-forming compound may be used in either a dispersed state or a dissolved state, and the salt-forming compound is used alone or in combination of two or more at any ratio as necessary. be able to. The salt-forming compound in the laser welding resin composition can be adjusted as necessary, but the content of the salt-forming compound with respect to 100 parts by weight of the thermoplastic resin is about 0.00001 to 0.4 parts by weight. Is preferable, about 0.0001 to 0.2 parts by weight is more preferable, and about 0.0001 to 0.02 parts by weight is further preferable.

  The resin composition for laser welding may contain other components in addition to the salt-forming compound and the resin.

(Other ingredients)
The laser welding resin composition is a composition containing a salt-forming compound and a thermoplastic resin, but contains any components in addition to the salt-forming compound and the thermoplastic resin as long as the effects of the present invention are not impaired. May be. Optional components include near infrared absorbing dyes other than salt-forming compounds, colorants, fillers, elastomers, stabilizers, mold release agents, UV absorbers, antistatic agents, antifogging agents, lubricants, antiblocking agents, plasticizers In addition, various additives such as a dispersant, an antibacterial agent, and a polymerization initiator may be contained.

  When these optional additives are used, the amount used thereof may be used in a range that is usually used as long as the effects of the present invention are not impaired, but preferably, with respect to 100 parts by weight of the thermoplastic resin. About 0.005 to 100 parts by weight, more preferably about 0.01 to 50 parts by weight is used.

(Production method of resin composition for laser welding)
There is no restriction | limiting in particular as a manufacturing method of the resin composition for laser welding of this invention, For example, the following method can be illustrated:
(A) A thermoplastic resin (powder, granules, flakes or pellets), the salt-forming compound of the present invention and, if necessary, the above-mentioned additives are mixed using a conventional mixer to dry-dry thermoplastic. A method for producing a resin composition,
(B) This dry blend type thermoplastic resin composition is melt-kneaded at a desired temperature using a conventional kneader, such as a uniaxial or biaxial extruder, and the extruded strand is cooled. Next, a method for producing a pellet type thermoplastic resin composition by cutting the cooled strand,
(C) A method for producing a master batch pellet type thermoplastic resin composition having a high content of the salt-forming compound of the present invention.

  Moreover, it is also possible to prepare the thermoplastic resin composition of the present invention without mixing each component in advance or by mixing only a part of the components in advance and supplying them to an extruder using a feeder and melt-kneading them. The resin composition for laser welding may be used for molding as it is, but the salt-forming compound is melted together with the thermoplastic resin and pelletized after kneading to obtain a master batch having a high salt-forming compound concentration. It may be diluted with resin, melted, kneaded and molded. The resin composition for laser welding of the present invention may be added with a fibrous reinforcing filler such as glass fiber, and when added, it can be supplied from the side feeder in the middle of the cylinder of the extruder. . The heating temperature at the time of melt kneading is not particularly limited as long as the temperature at which the thermoplastic resin melts, and can be appropriately selected from a range of 180 to 350 ° C, for example.

(Transparency of resin molding)
A resin molding can be manufactured from the resin composition for laser welding. As the resin molded body, one having a visible light transmittance of 80% or more can be obtained. Preferably it is 85% or more, More preferably, it is 90% or more. At this time, the resin molded body has an absorption maximum in the near infrared region of 750 to 850 nm, and the near infrared transmittance of 808 nm is in the range of 50 ± 5%. As with coating, the transmittance in the near-infrared region and visible light region can be controlled by changing the concentration of the resin composition for laser welding, and can be used for various laser strengths and welding applications. can do.

  When the resin molded body is applied industrially, it is preferable that the color tone of the resin molded body has a high visible light transmittance from the viewpoint that the color tone can be variously adjusted by a colorant.

  The shape of the resin molded body can be formed into an arbitrary shape as necessary, and can be formed into a more complicated shape in addition to a flat shape and a curved shape. In addition, the thickness of the light-absorbing resin molded body can be arbitrarily adjusted to a film shape, a plate shape, or the like, and the molded body once formed can be formed into an arbitrary complicated shape by post-processing.

(Production method of resin molding)
The method for producing the resin molded body is not particularly limited, and a molding method generally employed in the thermoplastic resin composition can be arbitrarily adopted. For example, (1) a method in which a thermoplastic resin and the salt-forming compound of the present invention are mixed and then melt-kneaded and then molded, and (2) a thermoplastic resin, the salt-forming compound of the present invention, and a polymerization initiator are molded. Examples of the method include polymerization in a frame and molding. The molding method is not particularly limited. For example, an injection molding method (including gas injection molding), an ultra-high speed injection molding method, an injection compression molding method (press injection), a two-color molding method, a gas molding and other hollow molding method. , Molding method using heat insulation mold, molding method using rapid heating mold, foam molding (including supercritical fluid), insert molding, IMC (in-mold coating molding) molding method, extrusion molding method, hollow molding, Known molding methods such as a calendar molding method, a sheet molding method, a film molding method, a thermoforming method, a rotational molding method, a laminate molding method, a press molding method, and a blow molding method are exemplified, and among them, injection molding is preferable.

  Examples of the apparatus for producing the resin molded body include known melt-kneading apparatuses such as a single screw extruder, a twin screw extruder, a Banbury mixer, a roll kneader, a kneader, and a Brabender plastograph.

<Laser welding>
Laser welding can be performed using the resin composition for laser welding of the present invention. In laser welding, resin members (joining members) are welded to each other by laser irradiation, and the resin composition for laser welding may be applied to a portion of the molded member (joining member) to be joined. However, it may be used by being kneaded into the molded member itself (joining member itself).

  In the case of method 1, the joining member uses a light transmissive resin. A laser welding resin layer is formed by applying a laser welding resin composition to a portion of the joining member to be joined, the joining members are overlapped via the laser welding resin layer, and laser irradiation is performed from one of the joining members. When this is done, the salt-forming compound generates heat, heat is transmitted from the vicinity of the generated salt-forming compound to the side of the joining member, the joining members melt, and joining is performed.

  In the case of method 2, one of the joining members is usually a light transmissive resin member (transmissive member), and the other is composed of a light absorbing resin member (absorbing member) that absorbs laser light and generates heat. In addition, when laser irradiation is performed on both the overlapped members from the transparent member side, the absorbent member is dissolved, and heat is transferred from the periphery of the dissolved absorbent member to the transparent member side to dissolve the transparent member. Occurs and bonding is performed.

  The laser beam used for laser welding is not particularly limited as long as it is a near-infrared laser beam, and examples thereof include a laser beam such as a semiconductor laser, a dye (pulse) laser, and an alexandrite laser.

  Since the maximum absorption wavelength of the laser welding resin composition of the present invention is in the range of 750 to 850 nm, the wavelength of the laser beam is preferably 750 to 850 nm, and more preferably 808 nm.

  Moreover, it is preferable that the output of a laser beam is 5-100W. If the output of the laser beam is less than 5 W, the output is low and it becomes difficult to melt the joint surfaces of the members. If the output exceeds 100 W, the output becomes excessive and the member evaporates or deteriorates. Moreover, the output of a laser beam can select an appropriate value according to the density | concentration of the resin composition for laser welding of this invention, the film thickness of a coating film, etc.

<Laser welded body>
The shape, size, thickness, etc. of the welded body that has been laser-welded are arbitrary. Applications of the welded body include parts for transportation equipment such as automobiles, parts for electrical and electronic equipment, parts for industrial machinery, and other consumer parts. Particularly preferred.

  EXAMPLES The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the following examples unless it exceeds the gist. In Examples and Comparative Examples, “part” and “%” mean “part by mass” and “% by mass”, respectively.

(Identification method of squarylium [A])
Elemental analysis and MALDI TOF-MS spectrum were used for identification of squarylium [A] used in the present invention. Elemental analysis was performed using a Perkin Elmer 2400 CHN Elegant Analyzer. The MALDI TOF-MS spectrum uses the MALDI mass spectrometer “autoflex III” manufactured by Bruker Daltonics, Inc. to identify the obtained compound with the coincidence between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. It was.

(Weight average molecular weight (Mw) of resin [B] having a cationic group in the side chain, resin type dispersant and binder resin)
The weight average molecular weight (Mw) of the resin [B] having a cationic group in the side chain used in the present invention, the resin-type dispersant, and the binder resin was a TSKgel column (manufactured by Tosoh Corporation) and equipped with an RI detector. It is a weight average molecular weight (Mw) in terms of polystyrene measured by GPC (manufactured by Tosoh Corporation, HLC-8120GPC) using THF as a developing solvent.

(Resin [B] having cationic group in side chain and quaternary ammonium salt value of resin-type dispersant)
The resin [B] having a cationic group in the side chain used in the present invention and the quaternary ammonium salt value of the resin-type dispersant were titrated with a 0.1N silver nitrate aqueous solution using a 5% potassium chromate aqueous solution as an indicator. After obtaining, it was converted to the equivalent of potassium hydroxide. The quaternary ammonium salt value of the following resin [B] indicates the quaternary ammonium salt value of the solid content.

(Amine number of resin-type dispersant)
The amine value of the resin-type dispersant was determined by potentiometric titration using a 0.1N hydrochloric acid aqueous solution, and then converted to an equivalent of potassium hydroxide. The amine value of the resin-type dispersant indicates the amine value of the solid content.

(Acid value of resin-type dispersant and binder resin)
The acid values of the resin-type dispersant and the binder resin were determined by potentiometric titration using a 0.1N potassium hydroxide / ethanol solution. The acid value of the resin and the resin-type dispersant indicates the acid value of the solid content.

<Method for producing squarylium [A]>
(Manufacture of squarylium [A-1])
To 400 parts of toluene, 40.0 parts of 1,8-diaminonaphthalene, 25.1 parts of cyclohexanone, and 0.087 part of p-toluenesulfonic acid monohydrate are mixed, heated and stirred in an atmosphere of nitrogen gas, 3 Reflux for hours. Water generated during the reaction was removed from the system by azeotropic distillation. After completion of the reaction, the dark brown solid obtained by distilling toluene was extracted with acetone and purified by recrystallization from a mixed solvent of acetone and ethanol. The obtained brown solid was dissolved in a mixed solvent of 240 parts of toluene and 160 parts of n-butanol, 13.8 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione was added, and an atmosphere of nitrogen gas was added. The mixture was heated and stirred in, and refluxed for 8 hours. Water generated during the reaction was removed from the system by azeotropic distillation. After completion of the reaction, the solvent was distilled off, and 200 parts of hexane was added while stirring the obtained reaction mixture. The resulting black-brown precipitate was filtered off, washed successively with hexane, ethanol and acetone and dried under reduced pressure. The obtained black-brown solid was dissolved in 1000 parts of 90% sulfuric acid and stirred at 30 degrees for 5 hours. After completion of the reaction, the reaction solution was added dropwise to 10000 parts of water while stirring, and the mixture was stirred at 20 degrees for 1 hour. The resulting precipitate was filtered off, washed with 0.5% hydrochloric acid and dried under reduced pressure to obtain 70.9 parts of squarylium [A-1] (yield: 92%). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-1].

Squarylium [A-1]

(Manufacture of squarylium [A-2])
The same operation as the production of squarylium [A-1] was carried out except that 1000 parts of 98% sulfuric acid was used instead of 1000 parts of 90% sulfuric acid used in the production of squarylium [A-1]. 2] 79.8 parts (yield: 92%) were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-2].

Squarylium [A-2]

(Manufacture of squarylium [A-3])
The same operation as the production of squarylium [A-1] was performed except that 1000 parts of 101% sulfuric acid was used instead of 1000 parts of 90% sulfuric acid used in the production of squarylium [A-1]. 3] 87.8 parts (yield: 91%) were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-3].

Squarylium [A-3]

(Manufacture of squarylium [A-4])
The same operation as the production of squarylium [A-1] was performed except that 1000 parts of 104.5% sulfuric acid was used instead of 1000 parts of 90% sulfuric acid used in the production of squarylium [A-1]. A-4] 95.6 parts (yield: 90%) were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-4].

Squarylium [A-4]

(Manufacture of squarylium [A-5])
The same operation as in the production of squarylium [A-2] was performed except that 32.2 parts of 2,6-dimethylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. , 89.8 parts (yield: 96%) of squarylium [A-5] were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-5].

Squarylium [A-5]

(Production of squarylium [A-6])
The same operation as in the production of squarylium [A-1] was performed except that 32.2 parts of 3,5-dimethylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-1]. , 82.2 parts (yield: 98%) of squarylium [A-6] was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-6].

Squarylium [A-6]

(Manufacture of squarylium [A-7])
The same operation as in the production of squarylium [A-2] was performed except that 32.2 parts of 3,5-dimethylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. , 90.8 parts of squarylium [A-7] (yield: 97%) were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-7].

Squarylium [A-7]

(Manufacture of squarylium [A-8])
The same operation as in the production of squarylium [A-3] was carried out except that 32.2 parts of 3,5-dimethylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-3]. , 98.1 parts (yield: 95%) of squarylium [A-8] were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-8].

Squarylium [A-8]

(Manufacture of squarylium [A-9])
The same operation as in the production of squarylium [A-4] was carried out except that 32.2 parts of 3,5-dimethylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-4]. , 106.2 parts (yield: 94%) of squarylium [A-9] were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-9].

Squarylium [A-9]

(Manufacture of squarylium [A-10])
The same operation as the production of squarylium [A-2] was carried out except that 28.6 parts of 4-methylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. [A-10] 85.6 parts (yield: 95%) were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-10].

Squarylium [A-10]

(Manufacture of squarylium [A-11])
The same operation as the production of squarylium [A-1] except that 35.8 parts of 3,3,5-trimethylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-1]. To obtain 81.1 parts of squarylium [A-11] (yield: 93%). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-11].

Squarylium [A-11]

(Manufacture of squarylium [A-12])
The same operation as the production of squarylium [A-2] except that 35.8 parts of 3,3,5-trimethylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. To obtain 90.2 parts (yield: 93%) of squarylium [A-12]. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-12].

Squarylium [A-12]

(Manufacture of squarylium [A-13])
The same operation as the production of squarylium [A-3] except that 35.8 parts of 3,3,5-trimethylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-3]. To obtain 98.1 parts of squarylium [A-13] (yield: 92%). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-13].

Squarylium [A-13]

(Manufacture of squarylium [A-14])
The same operation as the production of squarylium [A-4] except that 35.8 parts of 3,3,5-trimethylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-4]. To obtain 104.8 parts of squarylium [A-14] (yield: 90%). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-14].

Squarylium [A-14]

(Manufacture of squarylium [A-15])
The same operation as in the production of squarylium [A-1] was carried out except that 39.4 parts of 3,5-diethylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-1]. , 86.1 parts (yield: 95%) of squarylium [A-15] were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-15].

Squarylium [A-15]

(Manufacture of squarylium [A-16])
The same operation as in the production of squarylium [A-2] was conducted except that 39.4 parts of 3,5-diethylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. , 94.3 parts of squarylium [A-16] (yield: 94%) were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-16].

Squarylium [A-16]

(Manufacture of squarylium [A-17])
The same operation as in the production of squarylium [A-3] was carried out except that 39.4 parts of 3,5-diethylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-3]. , 103.5 parts of squarylium [A-17] (yield: 94%) were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-17].

Squarylium [A-17]

(Manufacture of squarylium [A-18])
The same operation as in the production of squarylium [A-4] was carried out except that 39.4 parts of 3,5-diethylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-4]. , 110.2 parts (yield: 92%) of squarylium [A-18] were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-18].

Squarylium [A-18]

(Manufacture of squarylium [A-19])
The same operation as the production of squarylium [A-2] except that 39.4 parts of 5-isopropyl-2-methylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. And 93.3 parts of squarylium [A-19] (yield: 93%) were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-19].

Squarylium [A-19]

(Manufacture of squarylium [A-20])
The same operation as in the production of squarylium [A-2] was conducted except that 46.0 parts of 2-cyclohexylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. [A-20] 97.1 parts (yield: 91%) were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-20].

Squarylium [A-20]

(Manufacture of squarylium [A-21])
Except for using 28.1 parts of 2-norbornanone instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2], the same operation as in the production of squarylium [A-2] was performed. A-21] was obtained 82.5 parts (yield: 92%). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-21].

Squarylium [A-21]

(Production of squarylium [A-22])
The production of squarylium [A-2] was performed except that 42.5 parts of spiro [5.5] undecan-1-one was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. The same operation was performed to obtain 97.1 parts of squarylium [A-22] (yield: 94%). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-22].

Squarylium [A-22]

(Manufacture of squarylium [A-23])
Instead of 25.1 parts of cyclohexanone used in the preparation of squarylium [A-2], 41.9 parts of 3-methyl-3,4,4a, 5,8,8a-hexahydronaphthalen-1 (2H) -one Was used in the same manner as in the production of squarylium [A-2] to obtain 93.5 parts of squarylium [A-23] (yield: 94%). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-23].

Squarylium [A-23]

(Manufacture of squarylium [A-24])
The same operation as the production of squarylium [A-2] except that 41.0 parts of 3- (2-chloroethyl) cyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. To obtain 95.8 parts of squarylium [A-24] (yield: 94%). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-24].

Squarylium [A-24]

(Manufacture of squarylium [A-25])
The production of squarylium [A-2] was performed except that 59.8 parts of 3,5-di (trifluoromethyl) cyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. The same operation was performed to obtain 111.4 parts of squarylium [A-25] (yield: 93%). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-25].

Squarylium [A-25]

(Manufacture of squarylium [A-26])
The same operation as the production of squarylium [A-2] was carried out except that 44.5 parts of 2-phenylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. [A-26] 96.8 parts (yield: 92%) were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-26].

Squarylium [A-26]

(Manufacture of squarylium [A-27])
The same operation as in the production of squarylium [A-2] was carried out except that 48.1 parts of 4-p-tolylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. , 102.1 parts of squarylium [A-27] (yield: 94%) were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-27].

Squarylium [A-27]

(Manufacture of squarylium [A-28])
The same operation as the production of squarylium [A-2] was carried out except that 48.1 parts of 4-benzylcyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. [A-28] 103.2 parts (yield: 95%) were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-28].

Squarylium [A-28]

(Manufacture of squarylium [A-29])
The same operation as the production of squarylium [A-2] was carried out except that 36.3 parts of 4-ethoxycyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. [A-29] 88.7 parts (yield: 91%) were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-29].

Squarylium [A-29]

(Manufacture of squarylium [A-30])
The production of squarylium [A-2] was performed except that 68.0 parts of 2,6-di (trifluoromethoxy) cyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. The same operation was performed to obtain 118.6 parts (yield: 93%) of squarylium [A-30]. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-30].

Squarylium [A-30]

(Manufacture of squarylium [A-31])
The same operation as the production of squarylium [A-2] was carried out except that 48.6 parts of 4-phenoxycyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. [A-31] 100.4 parts (yield: 92%) were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-31].

Squarylium [A-31]

(Manufacture of squarylium [A-32])
Production of squarylium [A-2] except that 52.4 parts of N-ethyl-3-oxocyclohexane-1-sulfoamide was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. The same operation was carried out to obtain 106.0 parts of squarylium [A-32] (yield: 94%). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-32].

Squarylium [A-32]

(Manufacture of squarylium [A-33])
The same operation as in the production of squarylium [A-2] was performed except that 36.3 parts of 4-oxocyclohexanecarboxylic acid was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. , 87.7 parts (yield: 90%) of squarylium [A-33] were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-33].

Squarylium [A-33]

(Manufacture of squarylium [A-34])
The same operation as in the production of squarylium [A-2] was conducted except that 43.5 parts of ethyl 2-oxocyclohexanecarboxylate was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. And 96.9 parts of squarylium [A-34] (yield: 93%) were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-34].

Squarylium [A-34]

(Manufacture of squarylium [A-35])
Similar to the production of squarylium [A-2] except that 46.8 parts of 4-oxo-N-propylcyclohexanecarboxamide were used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. Then, squarylium [A-35] 102.0 (yield: 95%) was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-35].

Squarylium [A-35]

(Manufacture of squarylium [A-36])
The same operation as the production of squarylium [A-2] was carried out except that 28.9 parts of 4-aminocyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. [A-36] 85.0 parts (yield: 94%) were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-36].

Squarylium [A-36]

(Manufacture of squarylium [A-37])
The same operation as in the production of squarylium [A-2] was conducted except that 36.1 parts of 4- (dimethylamino) cyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. And 92.3 parts (yield: 95%) of squarylium [A-37] were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-37].

Squarylium [A-37]

(Manufacture of squarylium [A-38])
The same operation as in the production of squarylium [A-2] was carried out except that 31.4 parts of 4-oxocyclohexanecarbonitrile was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. , 85.4 parts of squarylium [A-38] (yield: 92%). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-38].

Squarylium [A-38]

(Manufacture of squarylium [A-39])
The same operation as the production of squarylium [A-2] was carried out except that 36.6 parts of 4-nitrocyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. [A-39] 89.9 parts (yield: 92%) were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-39].

Squarylium [A-39]

(Manufacture of squarylium [A-40])
The same operation as in the production of squarylium [A-2] was conducted except that 34.3 parts of 3,5-difluorocyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. , 88.8 parts of squarylium [A-40] (yield: 93%) were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-40].

Squarylium [A-40]

(Manufacture of squarylium [A-41])
The same operation as the production of squarylium [A-2] was carried out except that 33.9 parts of 2-chlorocyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. [A-41] 87.5 parts (yield: 92%) were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-41].

Squarylium [A-41]

(Manufacture of squarylium [A-42])
The same operation as in the production of squarylium [A-2] was carried out except that 65.4 parts of 3,3-dibromocyclohexanone was used instead of 25.1 parts of cyclohexanone used in the production of squarylium [A-2]. , 116.3 parts (yield: 93%) of squarylium [A-42] were obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as squarylium [A-42].

Squarylium [A-42]

Tables 1 and 2 show the results of mass spectrometry and elemental analysis of squarylium [A-1] to [A-42] synthesized in the production examples.

<Preparation Method of Resin [B] Having Cationic Group in Side Chain>
(Preparation of resin [B-1] having a cationic group in the side chain)
Into a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, 67.3 parts of methyl ethyl ketone was charged and heated to 75 ° C. under a nitrogen stream. Separately, 33.2 parts of methyl methacrylate, 27.3 parts of n-butyl methacrylate, 27.3 parts of 2-ethylhexyl methacrylate, 12.2 parts of dimethylaminoethyl methyl chloride salt, 2,2′-azobis (2,4 -Dimethylvaleronitrile) 6.5 parts and 21.5 parts of methyl ethyl ketone were homogenized, charged into a dropping funnel, attached to a four-necked separable flask, and dropped over 2 hours. Two hours after the completion of dropping, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 7500, and the mixture was cooled to 50 ° C. Thereafter, 72 parts of isopropyl alcohol was added to obtain a resin [B-1] having a cationic group in the side chain of 40% by weight of the resin component. The ammonium salt value of the obtained resin was 33 mgKOH / g.

(Preparation of resin [B-2] having a cationic group in the side chain)
Into a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, 67.3 parts of methyl ethyl ketone was charged and heated to 75 ° C. under a nitrogen stream. Separately, 22.4 parts of methyl methacrylate, 16.7 parts of n-butyl methacrylate, 27.3 parts of 2-ethylhexyl methacrylate, 15.0 parts of hydroxyethyl methacrylate, 2.5 parts of methacrylic acid, 1.3 parts of t-butyl methacrylate 1.3 parts of isobutyl methacrylate, 1.3 parts of cyclohexyl methacrylate, 12.2 parts of dimethylaminoethyl methyl chloride salt, 6.5 parts of 2,2′-azobis (2,4-dimethylvaleronitrile), and After making 25.1 parts of methyl ethyl ketone uniform, it was charged in a dropping funnel, attached to a four-necked separable flask, and dropped over 2 hours. Two hours after the completion of the dropwise addition, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 7950, and the mixture was cooled to 50 ° C. Thereafter, 72 parts of isopropyl alcohol was added to obtain a resin [B-2] having a cationic group in the side chain of 40% by weight of the resin component. The ammonium salt value of the obtained resin was 33 mgKOH / g.

(Preparation of resin [B-3] having a cationic group in the side chain)
Into a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, 67.3 parts of methyl ethyl ketone was charged and heated to 75 ° C. under a nitrogen stream. Separately, 21.0 parts of methyl methacrylate, 27.3 parts of n-butyl methacrylate, 27.3 parts of 2-ethylhexyl methacrylate, 22.4 parts of dimethylaminoethyl methyl chloride salt, 2,2′-azobis (2,4 -Dimethylvaleronitrile) 6.5 parts and 21.5 parts of methyl ethyl ketone were homogenized, charged into a dropping funnel, attached to a four-necked separable flask, and dropped over 2 hours. Two hours after the completion of the dropwise addition, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 7640, and the mixture was cooled to 50 ° C. Thereafter, 72 parts of isopropyl alcohol was added to obtain a resin [B-3] having a cationic group in the side chain of 40% by weight of the resin component. The ammonium salt value of the obtained resin was 66 mgKOH / g.

(Preparation of resin [B-4] having a cationic group in the side chain)
Into a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, 62.4 parts of isopropyl alcohol was charged and heated to 75 ° C. under a nitrogen stream. Separately, 16.0 parts of methyl methacrylate, 17.0 parts of butyl methacrylate, 16.0 parts of styrene, 51.0 parts of dimethylaminoethyl methyl chloride salt, 2,2′-azobis (2,4-dimethylvaleronitrile) 6 parts and 25.0 parts of methyl ethyl ketone were homogenized, charged into a dropping funnel, attached to a four-necked separable flask, and dropped over 2 hours. Two hours after the completion of the dropping, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 7050, and the mixture was cooled to 50 ° C. Thereafter, 65 parts of isopropyl alcohol was added to obtain a resin [B-7] having a cationic group in the side chain of 40% by weight of the resin component. The ammonium salt value of the obtained resin was 138 mgKOH / g.

(Preparation of resin [B-5] having a cationic group in the side chain)
Into a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, 62.4 parts of isopropyl alcohol was charged and heated to 75 ° C. under a nitrogen stream. Separately, 35.5 parts of methyl methacrylate, 30.0 parts of butyl methacrylate, 16.8 parts of 2-ethylhexyl acrylate, 17.7 parts of dimethylaminopropylmethyl chloride methacrylate, 2,2′-azobis (2,4-dimethyl) 5.7 parts of valeronitrile) and 15.6 parts of methyl ethyl ketone were homogenized, charged into a dropping funnel, attached to a four-necked separable flask, and dropped over 2 hours. Two hours after the completion of the dropwise addition, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 7420, and the mixture was cooled to 50 ° C. Thereafter, 72 parts of isopropyl alcohol was added to obtain a resin [B-2] having a cationic group in the side chain of 40% by weight of the resin component. The ammonium salt value of the obtained resin was 45 mgKOH / g.

(Preparation of resin [B-6] having a cationic group in the side chain)
Into a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, 67.3 parts of methyl ethyl ketone was charged and heated to 75 ° C. under a nitrogen stream. Separately, 34.7 parts of isobornyl methacrylate, 1.7 parts of n-butyl methacrylate, 30.0 parts of hydroxyethyl methacrylate, 2.5 parts of methacrylic acid, 16.3 parts of t-butyl methacrylate, 2.5 parts of isobutyl methacrylate , 2.3 parts of cyclohexyl methacrylate, 10.0 parts of dimethylaminoethyl methacrylate, 6.5 parts of 2,2′-azobis (2,4-dimethylvaleronitrile), and 25.1 parts of methyl ethyl ketone, The mixture was placed in a dropping funnel, attached to a four-necked separable flask, and dropped over 2 hours. Two hours after the completion of the dropwise addition, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 6830, and the mixture was cooled to 50 ° C. To this, 3.2 parts of methyl chloride and 22.0 parts of ethanol were added, reacted at 50 ° C. for 2 hours, heated to 80 ° C. over 1 hour, and further reacted for 2 hours. Thus, a resin [B-6] having a cationic group in the side chain of 47% by weight of the resin component was obtained. The ammonium salt value of the obtained resin was 34 mgKOH / g.

(Preparation of resin [B-7] having a cationic group in the side chain)
Into a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, 67.3 parts of methyl ethyl ketone was charged and heated to 75 ° C. under a nitrogen stream. Separately, 60.0 parts of methyl methacrylate, 10.0 parts of n-butyl methacrylate, 10.0 parts of 2-isocyanatoethyl methacrylate, 20.0 parts of N, N-dimethylaminomethylstyrene, 2,2′-azobis (2 , 4-dimethylvaleronitrile) and 25.1 parts of methyl ethyl ketone were made uniform, charged in a dropping funnel, attached to a four-necked separable flask, and dropped over 2 hours. Two hours after the completion of the dropping, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 6770, and the mixture was cooled to 50 ° C. To this, 15.7 parts of benzyl chloride and 22.0 parts of ethanol were added, reacted at 50 ° C. for 2 hours, heated to 80 ° C. over 1 hour, and further reacted for 2 hours. Thus, a resin [B-7] having a cationic group in the side chain of 50% by weight of the resin component was obtained. The ammonium salt value of the obtained resin was 60 mgKOH / g.

(Preparation of resin [B-8] having a cationic group in the side chain)
A 4-neck separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser was charged with 62.4 parts of isopropyl alcohol and heated to 75 ° C. under a nitrogen stream. Separately, 30.0 parts of methyl methacrylate, 20.0 parts of butyl methacrylate, 15.0 parts of hydroxyethyl methacrylate, 5.0 parts of methacrylic acid, 10.0 parts of styrene, 20.0 parts of N-vinylpyrrolidone, 2,2 ′ -After 4.7 parts of azobis (2,4-dimethylvaleronitrile) and 15.6 parts of isopropyl alcohol were made uniform, charged into a dropping funnel, attached to a four-necked separable flask and dropped over 2 hours. . Two hours after the completion of the dropwise addition, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 7550, and the mixture was cooled to 50 ° C. To this, 9.0 parts of methyl chloride and 22.0 parts of isopropyl alcohol were added, reacted at 50 ° C. for 2 hours, heated to 80 ° C. over 1 hour, and further reacted for 2 hours. Thereafter, 50 parts of isopropyl alcohol was added to obtain a resin [B-8] having a cationic group in the side chain of 44% by weight of the resin component. The ammonium salt value of the obtained resin was 92 mgKOH / g.

The composition, ammonium salt value, and weight average molecular weight of the resins [B-1] to [B-8] synthesized in the production examples are separately shown in Table 3.

Abbreviations in Table 3 are shown below.
MMA: methyl methacrylate n-BMA: n-butyl methacrylate 2-EHMA: 2-ethylhexyl methacrylate 2-EHA: 2-ethylhexyl acrylate HEMA: hydroxyethyl methacrylate MAA: methacrylate tBMA: t-butyl methacrylate IBMA: isobutyl methacrylate CHMA: cyclohexyl Methacrylate IBX: Isobornyl methacrylate St: Styrene MOI: 2-isocyanatoethyl methacrylate

<Method for producing salt-forming compound>
[Production Example 43]
(Production of salt-forming compound 1)
A salt-forming compound 1 composed of squarylium [A-1] and a resin [B-2] having a cationic group was produced by the following procedure. The resin [B-2] having a cationic group in the side chain of 51 parts is added to 2000 parts of water, sufficiently stirred and mixed, and then heated to 60 ° C. On the other hand, an aqueous solution in which 6.03 parts of squarylium [A-1] and 0.85 parts of sodium hydroxide are dissolved in 90 parts of water is prepared and added dropwise to the above resin solution little by little. After dropping, the mixture is stirred at 60 ° C. for 120 minutes to sufficiently react. In order to confirm the end point of the reaction, it was judged that a salt-forming compound was obtained with the reaction solution dropped onto the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer, and 21 parts of squarylium [A-1] and a cation are obtained. The salt-forming compound 1 consisting of the resin [B-2] having a functional group was obtained.

[Production Examples 44 to 84]
(Production of salt-forming compounds 2 to 42)
Hereinafter, the squarylium [A] and the resin [B] used in the production of the salt-forming compound 1 were changed in the same manner as the salt-forming compound 1 except that the compounds and amounts shown in Table 4 were changed. Got.

[Production Example 85]
(Production of salt-forming compound 43)
The salt formation compound 43 which consists of squarylium containing squarylium [A-7] and sodium ion (Z ^<+> ) and resin [B-1] which has a cationic group with the following procedure was manufactured.
The resin [B-1] having a cationic group in the side chain of 25.5 parts is added to 2000 parts of water, and the mixture is sufficiently stirred and mixed, and then heated to 60 ° C. On the other hand, an aqueous solution in which 3.66 parts of squarylium [A-7] and 0.85 parts of sodium hydroxide are dissolved in 90 parts of water is prepared and added dropwise to the above resin solution little by little. After dropping, the mixture is stirred at 60 ° C. for 120 minutes to sufficiently react. In order to confirm the end point of the reaction, it was judged that a salt-forming compound was obtained with the reaction solution dropped onto the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer, and 10 parts of squarylium [A-7] and a cation A salt-forming compound 43 comprising a resin [B-1] having a functional group and sodium ion (Z ⁺ ) was obtained.

[Production Example 86]
(Production of salt-forming compound 44)
In the following procedure, squarylium [A-7] and a squarylium containing tetrabutyl ammonium ion (Z ^+), salt-forming compound comprising a resin [B-1] and tetrabutylammonium ions (Z ⁺⁾ having a cationic group 44 was produced.
The resin [B-1] having a cationic group in the side chain of 25.5 parts is added to 2000 parts of water, and the mixture is sufficiently stirred and mixed, and then heated to 60 ° C. On the other hand, 3.66 parts of squarylium [A-7] and 55 parts of 10% tetrabutylammonium hydroxy aqueous solution are added to 90 parts of water, and the resulting solution is added dropwise little by little. After dropping, the mixture is stirred at 60 ° C. for 120 minutes to sufficiently react. In order to confirm the end point of the reaction, it was judged that a salt-forming compound was obtained with the reaction solution dropped onto the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer, and 13 parts of squarylium [A-7] and a cation are obtained. A salt-forming compound 44 composed of the resin [B-1] having a functional group and tetrabutylammonium ion (Z ⁺ ) was obtained.

<Method for Producing Near-Infrared Absorbing Compound Other Than the Present Invention>
[Production Example 87]
(Phthalocyanine [C])
The following phthalocyanine [C] was synthesized with reference to JP-A-2006-124964.

Phthalocyanine [C]

<Method for producing resin-type dispersant>
(Resin Dispersant Solution 1) Adsorbing group: aromatic carboxyl group In a reaction vessel equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer, 100 parts of methyl methacrylate and n-butyl acrylate were synthesized as the first stage synthesis. 100 parts and 40 parts of propylene glycol monomethyl ether acetate were charged and replaced with nitrogen gas. Heat the reaction vessel to 80 ° C, add 12 parts of 3-mercapto-1,2-propanediol, and then add 0.2 part of 2,2'-azobisisobutyronitrile in 20 portions. It was added every 30 minutes and reacted at 80 ° C. for 12 hours, and it was confirmed by solid content measurement that 95% had reacted. Next, as the synthesis of the second stage, 30 parts of pyromellitic anhydride, 190 parts of propylene glycol monomethyl ether acetate, and 0.40 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst. Was added and reacted at 120 ° C. for 7 hours. It was confirmed by titration that 98% or more of the acid anhydride had been half-esterified, and the reaction was completed. Thus, a resin-type dispersant solution having a poly (meth) acrylate skeleton having an acid value of 42 mgKOH / g per solid content and a non-volatile content of 40% by weight of a weight average molecular weight of 9,800 and having an aromatic carboxyl group. 1 was obtained.

(Resin Dispersant Solution 2) Adsorbing group: tertiary amino group In a reaction apparatus equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, 60 parts of methyl methacrylate, 20 parts of n-butyl methacrylate, 13 parts of tetramethylethylenediamine .2 parts were charged, and the mixture was stirred at 50 ° C. for 1 hour while flowing nitrogen, and the system was replaced with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 133 parts of PGMAc were charged, and the temperature was raised to 110 ° C. under a nitrogen stream to start polymerization of the first block. After polymerization for 4 hours, the polymerization solution was sampled and the solid content was measured, and it was confirmed that the polymerization conversion was 98% or more in terms of non-volatile content.
Next, 61 parts of PGMAc and 20 parts of dimethylaminoethyl methacrylate (hereinafter referred to as DM) as the second block monomer were added to this reaction apparatus, and the reaction was continued while maintaining a nitrogen atmosphere at 110 ° C. to continue the reaction. After 2 hours from the addition of dimethylaminoethyl methacrylate, the polymerization solution is sampled to measure the solid content, and converted from the nonvolatile content to confirm that the polymerization conversion rate of the second block is 98% or more. The polymerization was stopped by cooling.
Propylene glycol monomethyl ether acetate was added to the previously synthesized block copolymer solution so that the nonvolatile content was 40% by weight. Thus, a resin type having a tertiary amino group, which is a poly (meth) acrylate skeleton having an amine value per solid content of 71.4 mgKOH / g, a weight average molecular weight of 9900 (Mw), and a nonvolatile content of 40% by weight. Dispersant solution 2 was obtained.

(Resin Dispersant Solution 3) Adsorbing group: Quaternary ammonium base A reactor equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer, 60 parts of methyl methacrylate, 20 parts of n-butyl methacrylate, 13 parts of tetramethylethylenediamine .2 parts were charged, and the mixture was stirred at 50 ° C. for 1 hour while flowing nitrogen, and the system was replaced with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 133 parts of PGMAc were charged, and the temperature was raised to 110 ° C. under a nitrogen stream to start polymerization of the first block. After polymerization for 4 hours, the polymerization solution was sampled and the solid content was measured, and it was confirmed that the polymerization conversion was 98% or more in terms of non-volatile content.
Next, 61 parts of PGMAc and 25.6 parts of methacryloyloxyethyltrimethylammonium chloride aqueous solution (“Acryester DMC78” manufactured by Mitsubishi Rayon Co., Ltd.) as the second block monomer were charged into this reactor and maintained at 110 ° C. under a nitrogen atmosphere. The reaction was continued with stirring. After 2 hours from charging methacryloyloxyethyltrimethylammonium chloride, the polymerization solution is sampled to measure the solid content, and converted from the nonvolatile content to confirm that the polymerization conversion rate of the second block is 98% or more. The polymerization was stopped by cooling to room temperature.
Propylene glycol monomethyl ether acetate was added to the previously synthesized block copolymer solution so that the nonvolatile content was 40% by weight. Thus, a poly (meth) acrylate skeleton having a quaternary ammonium salt value of 45.4 mg KOH / g, a weight average molecular weight of 9800 (Mw) and a non-volatile content of 40% by weight per solid content, and a quaternary ammonium base. A resin-type dispersant solution 3 was obtained.

<Method for producing binder resin solution 1>
(Binder resin solution 1) Transparent acrylic resin 70.0 parts of cyclohexanone was charged in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirring device in a separable four-necked flask, and the temperature was raised to 80 ° C. to react. After substituting the inside of the container with nitrogen, 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, paracumylphenol ethylene oxide modified acrylate (manufactured by Toagosei Co., Ltd.) "Aronix M110") 7.4 parts and a mixture of 2,2'-azobisisobutyronitrile 0.4 parts were added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight of 26000. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. The methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. The binder resin solution 1 was prepared by adding.

<Manufacture of resin composition for laser welding: Method 1 (dissolution system)>
[Example 1]
(Manufacture of laser welding resin composition (S-1))
After uniformly stirring and mixing a mixture having the following composition, ultrasonic treatment was performed for 30 minutes, and after confirming complete dissolution, the mixture was filtered through a 0.5 μm filter, and the laser welding resin composition (S-1 ) Was produced.
Salt-forming compound 1: 10.0 parts Binder resin solution 1: 15.0 parts Propylene glycol monomethyl ether acetate: 75.0 parts

[Examples 2 to 44, Comparative Example 1]
(Production of laser welding resin compositions (S-2) to (S-45))
Hereinafter, except having changed the compound and solvent which were used by manufacture of the resin composition for laser welding (S-1) into the kind shown in Table 5, it is the same as that of the resin composition for laser welding (S-1), Laser welding resin compositions (S-2) to (S-45) were obtained.

<Manufacture of resin composition for laser welding: Method 1 (dispersion system)>
[Example 45]
(Manufacture of resin composition for laser welding (D-1))
After uniformly stirring and mixing a mixture having the following composition, the mixture was dispersed with an Eiger mill for 3 hours using zirconia beads having a diameter of 0.5 mm, filtered through a 0.5 μm filter, and a resin composition for laser welding (D- 1) was produced.
Salt-forming compound 1: 10.0 parts Resin-type dispersant solution 1: 7.5 parts Binder resin solution 1: 35.0 parts Propylene glycol monomethyl ether acetate: 47.5 parts

[Examples 46 to 88, Comparative Example 2]
(Production of laser welding resin compositions (D-2) to (D-45))
Hereinafter, except having changed into the kind shown in Table 6 the compound and resin type dispersing agent which were used by manufacture of the laser welding composition (D-1), it is the same as that of the laser welding resin composition (D-1). Thus, resin compositions for laser welding (D-2) to (D-45) were obtained.

<Coating process of resin composition for laser welding>
[Example 89]
(Coating process to molded member of resin composition for laser welding (S-1))
A 10 cm square, 1 mm thick polystyrene transparent plate was prepared, and the resin composition (S-1) for laser welding was applied to the surface of this polystyrene transparent plate using a bar coater, and then at 60 ° C. for 5 minutes. Oven dried. The film thickness at the time of coating was adjusted so that the near-infrared transmittance at the laser wavelength to be irradiated (in this case, 808 nm) was 50 ± 1%.

[Examples 90 to 176, Comparative Examples 3 and 4]
(Coating process of the resin composition for laser welding (S-2) to (S-45), (D-1) to (D-45) on a molded member)
Hereinafter, the laser welding resin composition (S-) except that the composition used in the coating process of the laser welding resin composition (S-1) to the molding member and the molding member were changed to the types shown in Table 7. In the same manner as 1), the laser welding resin compositions (S-2) to (S-45) and (D-1) to (D-45) were solid-coated on the molded member.

In addition, the transparent plate for each said coating was produced using the following thermoplastic resin.
PS: Polystyrene (trade name: CR-4500; manufacturer: DIC)
PMMA: Polymethylmethacrylate (trade name: Parapet HR-L; manufacturer: Kuraray)
COP: Cycloolefin polymer (trade name: ZEONEX E48R; manufacturer: Nippon Zeon)
PC: Polycarbonate (Product name: Iupilon H-4000; Manufacturer: Mitsubishi Engineering Plastics)

<Manufacture of resin composition for laser welding: Method 2>
[Example 177]
(Manufacture of laser welding composition (M-1) and its molded product)
As a thermoplastic resin, 100 parts by weight of polystyrene (trade name: CR-4500; manufacturer: DIC) and 0.1 part by weight of salt-forming compound 1 are mixed, and a twin-screw extruder (Laboplast Mill Micro manufactured by Toyo Seiki Seisakusho). Was melt-kneaded at an appropriate melting temperature of polystyrene (260 ° C.) and extruded into a string shape. The obtained string-like laser welding composition was cooled and cut to obtain a pellet-like masterbatch. Subsequently, this master batch and the said polystyrene were mixed, and it melt-kneaded at 260 degreeC using the twin-screw extruder, and obtained the pellet-shaped laser welding composition (M-1) similarly. This pellet-shaped laser welding composition (M-1) is molded at a cylinder temperature of 260 ° C. using a hot press machine (Azwan hot press machine AH-4015), and is a 10 cm square, 1 mm thick laser welding composition. A molded product of (M-1) was obtained. Master batch concentration when producing pellet-shaped laser welding composition (M-1) so that the near-infrared transmittance of the molded product at the laser wavelength to be irradiated (in this case, 808 nm) is 50 ± 1% Was prepared.

[Examples 178 to 220, Comparative Example 6]
(Production of laser welding resin compositions (M-2) to (M-45) and molded articles thereof)
The laser welding composition (M-1), the compound used in the production of the molded product, and the thermoplastic resin were changed to the types shown in Table 8 and were the same as the laser welding composition (M-1). The laser welding compositions (M-2) to (M-45) were produced, and the respective molded members were produced. The process temperature was changed according to the type of thermoplastic resin used.

<Evaluation results of resin composition for laser welding>
[Examples 178 to 352, Comparative Examples 6 to 8]
(Measurement method of near-infrared transmittance of resin composition for laser welding)
The transmission spectrum at the center of the coated plate and the molded product obtained by the above method was measured in the wavelength range of 300 to 900 nm using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation). Tables 9 to 11 show the transmittance at 808 nm as the near-infrared transmittance.

(Measurement method of average visible light transmittance of resin composition for laser welding)
The transmission spectrum at the center of the coated plate and the molded product obtained by the above method was measured in the wavelength range of 300 to 900 nm using a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation). Tables 9 to 11 show the average transmittance in the visible light region (400 to 700 nm).

(Evaluation of uniformity of resin composition for laser welding)
Using the spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation), the spectrophotometer U-4100 was randomly obtained by changing the measurement location in addition to the central location. The transmission spectrum in the wavelength range of 300-900 nm was measured. Based on the “difference between the maximum value and the minimum value” of the transmittance at 808 nm of a total of 10 points measured, it was evaluated whether the coated plate and the molded product were uniform. It can be said that the smaller the difference, the more uniform the coated plate and the molded product, the less welding unevenness at the time of laser welding, and the better the processability. The evaluation results are shown in Tables 9-11.
◎: Less than 0.2% ○: 0.2% or more, less than 1.0% △: 1.0% or more, less than 2.0% ×: 2.0% or more

(Laser welding method: Method 1)
“The polystyrene plate coated with the laser welding composition (S-1)” manufactured by the above method and the “polystyrene plate not coated with anything” prepared in advance are sandwiched between the coating layers. Overlapping and irradiating the overlapped part with laser light by selecting optimum conditions among laser wavelength 808nm, laser scanning speed 1-10mm / sec, laser output 10, 20, 30, 40, 50, 60W did. Regarding the laser welding compositions (S-2) to (S-45) and (D-1) to (D-45), the laser beam is irradiated in the same manner as the laser welding composition (S-1). did.

(Laser welding method: Method 2)
The “polystyrene plate kneaded with the laser welding composition (M-1)” produced by the above method and the “polystyrene plate kneaded with nothing” produced in advance were superposed. Optimum conditions were selected for the portion among the laser wavelength of 808 nm, the laser scanning speed of 1 to 10 mm / sec, and the laser output of 10, 20, 30, 40, 50, and 60 W, and laser light was irradiated. At this time, laser light was applied from the direction of “polystyrene plate with nothing kneaded = (light transmissive resin)”. Regarding the laser welding compositions (M-2) to (M-45), the laser beam was irradiated in the same manner as the laser welding composition (M-1) according to each molded member.

(Evaluation of welding strength of laser welded body)
The tips of the plates after laser irradiation were each grasped to determine the degree of welding. The results are shown in Tables 9-12.
○: Welded sufficiently ×: Not welded

Method 1 (dissolution system):

Method 1 (dispersion system):

Method 2:

The laser welding resin composition containing the salt-forming compound of the present invention further reduces absorption in the visible light region (400 to 700 nm), has extremely excellent processability and weldability, and is obtained by welding. The welding strength of the body was also shown to be very good. In particular, the resin composition for laser welding containing salt-forming compounds 6-9, 11-14, 43, 44 in which X ₃ , X ₄ , X ₇ and X ₈ of the cycloring of squarylium [A] are substituted with methyl groups Was a very good result. Among them, the laser welding resin composition having the salt-forming compounds 6, 7, 11, 12, 43, and 44 having a sulfo group substitution number n = 1 or 2 has particularly good results in terms of optical properties and processability. Met. On the other hand, the laser welding resin composition having a salt-forming compound with n = 3 or 4 was a result of slightly inferior visible light average transmittance and uniformity.

  Further, the salt-forming compounds 20, 28, and 36 using the resin [B-4] having an ammonium salt value of 130 mgKOH / g or more are poor in solubility and dispersibility in the resin and slightly inferior in average visible light transmittance. Met. In addition, the resin composition for laser welding containing the salt-forming compound of the present invention gave good results in both the coating type (dissolution system, dispersion system) and kneading type methods. From this, it can be said that the laser welding resin composition containing the salt-forming compound of the present invention does not depend on the process and has good performance as a laser welding application, that is, in any process. It can be said that it has excellent processability for practical use. In particular, since coating and dispersion can be performed uniformly, welding unevenness hardly occurs during welding, and the welding strength can be easily controlled by controlling the film thickness and concentration. On the other hand, the laser-welded resin composition containing phthalocyanine [C] which is not the present invention has good welding strength but is insufficient in transparency in the visible light region and uniform coatability / uniform dispersibility. As a result, applications and processes are very limited.

  The laser-welded resin composition thus produced further reduces the absorption in the visible light region (400 to 700 nm), has excellent processability and weldability, and is a welded body obtained by welding. It was also shown that the welding strength of was very good. Furthermore, it can be applied to both coating type and kneading type processes, and it can be said that it has excellent processability for practical use as well as performance as laser welding.

Claims (10)

A laser welding resin composition comprising a salt-forming compound of squarylium [A] represented by the following general formula (1) and a resin [B] having a cationic group in a side chain, and a resin.
General formula (1)

[In General Formula (1), X _{1 to} X ₁₀ each independently have a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a substituent. An aryl group which may have a substituent, an aralkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an amino group, a substituted amino group, —SO ₂ NR ₁ R ₂ , —COOR ₃ , —CONR ₄ R ₅ , a nitro group, a cyano group, or a halogen atom may be represented, and adjacent groups may form a ring. R _{1 to} R ₅ each independently represents a hydrogen atom or an alkyl group which may have a substituent. n represents an integer of 1 to 4. Z ⁺ represents a hydrogen ion or an inorganic or organic cation. ] The resin composition for laser welding according to claim 1, wherein the resin [B] having a cationic group in a side chain is a vinyl resin containing a structural unit represented by the following general formula (2).
General formula (2)

[In General Formula (2), R ₆ represents a hydrogen atom or an alkyl group which may have a substituent. R _{7 to} R ₉ each independently represent a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an aryl group that may have a substituent; Two of _{7 to} R ₉ may be bonded to each other to form a ring. Q represents an alkylene group, an arylene group, —CONH—R ₁₀ — or —COO—R ₁₁ —, and R ₁₀ and R ₁₁ represent an alkylene group. Y ⁻ represents an inorganic or organic anion. ]   The resin composition for laser welding according to claim 1 or 2, wherein n in the general formula (1) is 1 or 2.   The resin composition for laser welding according to any one of claims 1 to 3, wherein the resin is a binder resin having a weight average molecular weight (Mw) of 10,000 to 100,000.   A laser welding resin layer formed from the laser welding resin composition according to claim 1.   The resin layer for laser welding according to claim 5, wherein an average transmittance in a visible light region is 80% or more.   The laser welding resin layer according to claim 5 or 6, which has an absorption maximum in a near infrared region of 750 to 850 nm.   The joined body by which the 1st joining member, the laser welding resin layer as described in any one of Claims 5-7, and the 2nd joining member are joined by laser welding.   The manufacturing method of the conjugate | zygote which joins a 1st joining member, the laser welding resin layer as described in any one of Claims 5-7, and a 2nd joining member by irradiating a laser beam.   After the laser welding resin layer according to any one of claims 5 to 7 is formed on the first bonding member, the resin layer is bonded to the second bonding member and bonded by irradiating laser light. Manufacturing method of joined body.