JP2016117194A - Resin metal composite and manufacturing method therefor - Google Patents

Abstract

The present invention provides a resin-metal composite that is remarkably excellent in weldability between a polyester resin and a metal substrate. A second member made of a polyester resin composition (B) is laser-welded on a first member formed by laminating a layer made of a polyester resin (A) as a top layer on a metal substrate. A resin-metal composite characterized by the above. [Selection figure] None

Description

  The present invention relates to a resin-metal composite and a method for producing the same.

  In recent years, in automobile parts and consumer parts, from the environmental aspects such as weight reduction and recycling, parts made of metal have been made resin, and resin products have been downsized. Polyester resins are widely used in various equipment parts because they have excellent mechanical strength, chemical resistance, electrical insulation, etc., and have excellent heat resistance, moldability, and recyclability. . In particular, thermoplastic polyester resins represented by polybutylene terephthalate resin are widely used in electrical and electronic equipment parts that require fire safety because they are excellent in mechanical strength and moldability and can be made flame retardant. Has been.

Electrical and electronic equipment parts, automobile parts, and the like are usually combined with metals such as aluminum and iron and used as resin-metal composites. Compounding with a metal is advantageous from the viewpoint of antistatic, thermal conductivity, and electromagnetic wave shielding properties as well as improving strength.
In order to manufacture such a resin-metal composite, for example, as disclosed in Patent Document 1, a thermoplastic resin is in-mold-molded on a metal substrate to be integrally formed with a metal. However, a composite in which a thermoplastic polyester resin is formed on a metal substrate by in-mold molding has a drawback that adhesion between the thermoplastic polyester resin and the metal substrate is poor.

  As a method for obtaining a composite of a resin and a metal, a method of joining a resin by injection molding to a component obtained by subjecting a metal component to a surface treatment (see, for example, Patent Document 2) has been proposed. However, in this method, it is necessary to perform a specific surface treatment on the metal part, and the work becomes complicated, so that it is inefficient and it is difficult to obtain a stable bonding strength.

  In addition, in the techniques of Patent Documents 1 and 2, for example, when a resin having a complicated shape is combined with a metal, it cannot be welded due to a shape factor or sufficient welding strength can be obtained even if it can be welded. There is also a problem of not being.

JP-A-6-29669 JP 2008-173967 A

  An object (problem) of the present invention is to provide a resin-metal composite that is remarkably excellent in weldability between a polyester resin and a metal substrate.

As a result of intensive studies to solve the above problems, the present inventor has added a second member made of a polyester resin composition to a first member obtained by laminating a polyester resin as an outermost layer on a metal substrate. It has been found that a resin-metal composite with a significantly excellent weldability between the polyester resin and the metal substrate can be achieved by welding the outermost layer of the member with laser light, and the present invention has been achieved.
The present invention is as follows.

[1] A second member made of a polyester resin composition (B) is laser-welded on a first member formed by laminating a layer made of a polyester resin (A) on a metal substrate as an outermost layer. A resin-metal composite characterized by
[2] The resin metal composite according to [1], wherein the metal substrate is made of aluminum or iron. [3] The above [1], wherein the first member is a laminate in which a layer made of a polyester resin (A) is laminated as an outermost layer through an adhesive layer after a chemical conversion treatment is performed on a metal substrate. Or the resin metal composite according to [2].

[4] The polyester resin composition (B) contains a polybutylene terephthalate resin and a polyethylene terephthalate resin as the polyester resin (b), and the content of the polyethylene terephthalate resin is a total of 100 masses of the polybutylene terephthalate resin and the polyethylene terephthalate resin. The resin metal composite according to any one of [1] to [3], which is 10 to 50% by mass relative to%.
[5] The polyester resin composition (B) includes a polybutylene terephthalate resin and a modified polybutylene terephthalate resin as the polyester resin (b), and the content of the modified polybutylene terephthalate resin is the polybutylene terephthalate resin and the modified polybutylene. The resin metal composite according to any one of [1] to [3], which is 20 to 70% by mass relative to a total of 100% by mass of the terephthalate resin.
[6] The polyester resin composition (B) includes a polybutylene terephthalate resin and a polycarbonate resin as the polyester resin (b), and the content of the polycarbonate resin is 100% by mass in total of the polybutylene terephthalate resin and the polycarbonate resin. Resin metal composite in any one of said [1]-[3] which is 10-50 mass% with respect to.
[7] The polyester resin composition (B) contains, as the polyester resin (b), a polybutylene terephthalate resin, polystyrene and / or butadiene rubber-containing polystyrene and a polycarbonate resin, and a polybutylene terephthalate resin, polystyrene and / or butadiene. 30 to 90% by mass of polybutylene terephthalate resin, 1 to 50% by mass of polystyrene and / or butadiene rubber-containing polystyrene, and 1 to 50% by mass of polycarbonate resin, based on a total of 100% by mass of rubber-containing polystyrene and polycarbonate resin. The resin metal composite according to any one of the above [1] to [3].

[8] On the first member formed by laminating the layer made of the polyester resin (A) on the metal substrate as the outermost layer, the second member made of the polyester resin composition (B) is placed on the second member side. A method for producing a resin-metal composite, characterized in that welding is performed by irradiating with laser light.
[9] On the first member formed by laminating the layer made of the polyester resin (A) on the metal substrate as the outermost layer, the second member made of the polyester resin composition (B) is made of the first member. A method for producing a resin-metal composite comprising irradiating and welding a laser beam from a metal substrate side.

  The resin-metal composite of the present invention exhibits excellent laser welding processability and can achieve a laser welding molded article having excellent welding strength.

It is a schematic diagram of the ASTM No. 4 dumbbell piece for the second member used in the examples.

The resin-metal composite of the present invention comprises a second member made of a polyester resin composition (B) on a first member formed by laminating a layer made of a polyester resin (A) as a top layer on a metal substrate. It is formed by laser welding.
Moreover, the 1st manufacturing method of the resin metal composite of this invention is a polyester resin composition (B) on the 1st member formed by laminating | stacking the layer which consists of a polyester resin (A) on a metal base | substrate as an outermost layer. The second member is formed by welding with a laser beam from the second member side.
Furthermore, in the second method for producing the resin-metal composite of the present invention, a polyester resin composition (B) is formed on a first member obtained by laminating a layer made of a polyester resin (A) as a top layer on a metal substrate. The second member made of (2) is welded by irradiating a laser beam from the metal base side of the first member.

  Hereinafter, the contents of the present invention will be described in detail. The following description may be made based on representative embodiments and specific examples of the present invention, but the present invention is not construed as being limited to such embodiments and specific examples.

  The resin-metal composite of the present invention is a resin obtained by integrally welding a member made of a polyester resin composition (B) opposite to a laminate obtained by laminating a polyester resin (A) as a top layer on a metal substrate by laser welding. And a metal composite, which is a resin metal composite in which a metal and a polyester resin are firmly bonded. The present invention uses a first member in which a polyester resin layer is laminated on a metal substrate as the outermost layer while being a polyester resin and metal, which are difficult to be firmly welded, and comprises a polyester resin composition (B). By superimposing the second member on the outermost layer of the polyester resin (A) of the first member and irradiating with laser light, the metal and polyester resin are firmly laser-welded, and the first and first metal composite that is integrated and firmly bonded It is possible.

[Second member]
The member made of the polyester resin composition (B) used as the second member can be produced by any molding method such as injection molding or extrusion molding of the polyester resin composition (B). The shape of the member is not particularly limited, but since the members are joined and used by laser welding, it is usually preferable to have a shape having at least a surface contactable surface, for example, a flat surface or a curved surface.

The polyester resin (b) which is the main component of the polyester resin composition (B) forming the second member contains a polyester resin, and preferably contains a polyester resin in a proportion of 50% by mass or more. Is.
The polyester resin is preferably a thermoplastic polyester resin obtained by polycondensation of a dicarboxylic acid compound and a dihydroxy compound, polycondensation of an oxycarboxylic acid compound or polycondensation of these compounds, and is either a homopolyester or a copolyester. May be.

As the dicarboxylic acid compound constituting the polyester resin, an aromatic dicarboxylic acid or an ester-forming derivative thereof is preferably used.
As aromatic dicarboxylic acids, terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, biphenyl-2,2′-dicarboxylic acid, Biphenyl-3,3′-dicarboxylic acid, biphenyl-4,4′-dicarboxylic acid, diphenyl ether-4,4′-dicarboxylic acid, diphenylmethane-4,4′-dicarboxylic acid, diphenylsulfone-4,4′-dicarboxylic acid Diphenylisopropylidene-4,4′-dicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4′-dicarboxylic acid, anthracene-2,5-dicarboxylic acid, anthracene-2,6-dicarboxylic acid, p -Terphenylene-4,4'-dicarboxylic acid, pyridine-2,5-dicarboxylic acid, etc. Refutaru acid can be preferably used.

These aromatic dicarboxylic acids may be used as a mixture of two or more. As is well known, these compounds can be used in polycondensation reactions with dimethyl esters or the like as ester-forming derivatives in addition to free acids.
If the amount is small, together with these aromatic dicarboxylic acids, aliphatic dicarboxylic acids such as adipic acid, azelaic acid, dodecanedioic acid, sebacic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid and 1 One or more alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid can be mixed and used.

Examples of the dihydroxy compound constituting the polyester resin include ethylene glycol, propylene glycol, butanediol, hexylene glycol, neopentyl glycol, 2-methylpropane-1,3-diol, diethylene glycol, triethylene glycol and other aliphatic diols, cyclohexane Examples include alicyclic diols such as -1,4-dimethanol, and mixtures thereof. If the amount is small, one or more kinds of long-chain diols having a molecular weight of 400 to 6,000, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, and the like may be copolymerized.
In addition, aromatic diols such as hydroquinone, resorcin, naphthalenediol, dihydroxydiphenyl ether, and 2,2-bis (4-hydroxyphenyl) propane can also be used.

  In addition to the above-mentioned bifunctional monomers, trifunctional monomers such as trimellitic acid, trimesic acid, pyromellitic acid, pentaerythritol, and trimethylolpropane are introduced to introduce a branched structure, and fatty acids are used for molecular weight control. A small amount of a monofunctional compound can be used in combination.

  As the polyester resin, a resin mainly comprising a polycondensation of a dicarboxylic acid and a diol, that is, a resin comprising 50% by mass, preferably 70% by mass or more of the entire resin, is used. The dicarboxylic acid is preferably an aromatic carboxylic acid, and the diol is preferably an aliphatic diol.

  Among them, polyalkylene terephthalate in which 95 mol% or more of the acid component is terephthalic acid and 95 mass% or more of the alcohol component is an aliphatic diol is preferable. Typical examples thereof are polybutylene terephthalate resin and polyethylene terephthalate resin. These are preferably close to homopolyester, that is, 95% by mass or more of the total resin is composed of a terephthalic acid component and a 1,4-butanediol or ethylene glycol component.

The intrinsic viscosity of the polyester resin is preferably 0.5 to 2 dl / g. From the viewpoint of moldability and mechanical properties, those having an intrinsic viscosity in the range of 0.6 to 1.5 dl / g are preferred. If the intrinsic viscosity is lower than 0.5 dl / g, the polyester resin composition (B) tends to have a low mechanical strength. If it is higher than 2 dl / g, the fluidity of the resin composition (B) may be deteriorated and the moldability may be deteriorated, or the laser weldability may be deteriorated.
In addition, the intrinsic viscosity of the polyester resin is a value measured at 30 ° C. in a 1: 1 (mass ratio) mixed solvent of tetrachloroethane and phenol.

  The terminal carboxyl group amount of the polyester resin may be appropriately selected and determined, but is usually 60 eq / ton or less, preferably 50 eq / ton or less, and more preferably 30 eq / ton or less. If it exceeds 50 eq / ton, gas tends to be generated during melt molding of the resin composition. Although the lower limit of the amount of terminal carboxyl groups is not particularly defined, it is usually 10 eq / ton.

  The terminal carboxyl group amount of the polyester resin is a value measured by dissolving 0.5 g of the polyester resin in 25 mL of benzyl alcohol and titrating with a 0.01 mol / l benzyl alcohol solution of sodium hydroxide. As a method for adjusting the amount of terminal carboxyl groups, a conventionally known arbitrary method such as a method for adjusting polymerization conditions such as a raw material charge ratio during polymerization, a polymerization temperature, a pressure reduction method, a method for reacting a terminal blocking agent, etc. Just do it.

It is preferable that 50 mass% or more in a polyester-type resin (b) is a polybutylene terephthalate resin.
The polyester resin (b) preferably contains a polybutylene terephthalate resin and a polyethylene terephthalate resin. When the polybutylene terephthalate resin and the polyethylene terephthalate resin are contained, the content of the polyterylene terephthalate resin and the polyethylene terephthalate resin is preferably 5 to 50% by mass with respect to the total 100% by mass of the polybutylene terephthalate resin and the polyethylene terephthalate resin. More preferably, it is 10-45 mass%, More preferably, it is 15-40 mass%. When the content of the polyethylene terephthalate resin is less than 5% by mass, the laser welding strength tends to decrease, and when it exceeds 50% by mass, the moldability may be significantly decreased.

  Polyethylene terephthalate resin is a resin mainly composed of oxyethyleneoxyterephthaloyl units composed of terephthalic acid and ethylene glycol with respect to all structural repeating units, and includes structural repeating units other than oxyethyleneoxyterephthaloyl units. Also good. The polyethylene terephthalate resin is produced using terephthalic acid or a lower alkyl ester thereof and ethylene glycol as main raw materials, but other acid components and / or other glycol components may be used together as raw materials.

  Acid components other than terephthalic acid include phthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 4,4′-diphenylsulfone dicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3- Examples thereof include phenylenedioxydiacetic acid and structural isomers thereof, dicarboxylic acids such as malonic acid, succinic acid and adipic acid and derivatives thereof, and oxyacids such as p-hydroxybenzoic acid and glycolic acid or derivatives thereof.

  Examples of diol components other than ethylene glycol include 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, aliphatic glycols such as pentamethylene glycol, hexamethylene glycol, and neopentyl glycol, cyclohexane Examples include alicyclic glycols such as dimethanol, and aromatic dihydroxy compound derivatives such as bisphenol A and bisphenol S.

  Further, from the viewpoint of laser weldability, as the polybutylene terephthalate resin, a modified polybutylene terephthalate resin obtained by copolymerization of polyalkylene glycol such as isophthalic acid, dimer acid or polytetramethylene glycol (PTMG) is also preferable.

When the isophthalic acid copolymerized polybutylene terephthalate resin is used as the modified polybutylene terephthalate resin, the proportion of the isophthalic acid component in the total carboxylic acid component is preferably 1 to 30 mol% as the carboxylic acid group, 20 mol% is more preferable, and 3 to 15 mol% is more preferable. By setting it as such a copolymerization ratio, it exists in the tendency which is excellent in the balance of laser weldability, heat resistance, injection moldability, and toughness, and is preferable.
When the polyester ether resin copolymerized with polytetramethylene glycol is used as the modified polybutylene terephthalate resin, the proportion of the tetramethylene glycol component in the copolymer is preferably 3 to 40% by mass, and 5 to 30% by mass. % Is more preferable, and 10 to 25% by mass is more preferable. By setting it as such a copolymerization ratio, it tends to be excellent in the balance between laser weldability and heat resistance, which is preferable.
When using a dimer acid copolymerized polybutylene terephthalate resin as the modified polybutylene terephthalate resin, the proportion of the dimer acid component in the total carboxylic acid component is preferably 0.5 to 30 mol% as the carboxylic acid group, 1-20 mol% is more preferable, and 3-15 mol% is further more preferable. By setting it as such a copolymerization ratio, it exists in the tendency which is excellent in the balance of laser weldability, long-term heat resistance, and toughness, and is preferable.

  Among the modified polybutylene terephthalate resins described above, a polyester ether resin copolymerized with polytetramethylene glycol and an isophthalic acid copolymerized polybutylene terephthalate resin are preferable from the viewpoint of laser weldability.

  The polyester-based resin (b) preferably includes a polybutylene terephthalate resin and the modified polybutylene terephthalate resin. When the polybutylene terephthalate resin and the modified polybutylene terephthalate resin are contained, the content is polybutylene terephthalate. The modified polybutylene terephthalate resin is preferably 10 to 70% by mass, more preferably 20 to 65% by mass, and further preferably 30 to 60% with respect to 100% by mass of the total of the resin and the modified polybutylene terephthalate resin. % By mass. When the content of the modified polybutylene terephthalate resin is less than 10% by mass, the laser welding strength tends to decrease. When the content exceeds 70% by mass, the moldability may be remarkably decreased.

It is also preferable that the polyester resin (b) contains a polybutylene terephthalate resin and a polycarbonate resin. By containing a specific amount of the polycarbonate resin, the laser weldability is easily improved, which is preferable.
The polycarbonate resin is an optionally branched thermoplastic polymer or copolymer obtained by reacting a dihydroxy compound or a small amount thereof with phosgene or a carbonic acid diester.

  As a dihydroxy compound as a raw material of the polycarbonate resin, an aromatic dihydroxy compound is preferable, and 2,2-bis (4-hydroxyphenyl) propane (that is, bisphenol A), tetramethylbisphenol A, bis (4-hydroxyphenyl) -p. -Diisopropylbenzene, hydroquinone, resorcinol, 4,4-dihydroxydiphenyl, etc. are mentioned, Preferably bisphenol A is mentioned. In addition, a compound in which one or more tetraalkylphosphonium sulfonates are bonded to the above aromatic dihydroxy compound can also be used.

  As the polycarbonate resin, among the above-mentioned, aromatic polycarbonate resin derived from 2,2-bis (4-hydroxyphenyl) propane, or 2,2-bis (4-hydroxyphenyl) propane and other aromatic dihydroxy Aromatic polycarbonate copolymers derived from the compounds are preferred. Further, it may be a copolymer mainly composed of an aromatic polycarbonate resin, such as a copolymer with a polymer or oligomer having a siloxane structure. Furthermore, you may mix and use 2 or more types of the polycarbonate resin mentioned above.

The viscosity average molecular weight of the polycarbonate resin is preferably 5,000 to 30,000, more preferably 10,000 to 28,000, and further preferably 14,000 to 24,000. When a material having a viscosity average molecular weight lower than 5,000 is used, the obtained welding member tends to have a low mechanical strength. If it is higher than 30,000, the fluidity of the resin composition may be deteriorated to deteriorate the moldability or the laser weldability may be lowered.
The viscosity average molecular weight of the polycarbonate resin is a viscosity average molecular weight [Mv] converted from a solution viscosity measured at a temperature of 25 ° C. using methylene chloride as a solvent.

  The ratio (Mw / Mn) of polystyrene-converted mass average molecular weight Mw and number average molecular weight Mn measured by gel permeation chromatography (GPC) of the polycarbonate resin is preferably 2 to 5, 2.5 ~ 4 is more preferred. When Mw / Mn is too small, the fluidity in the molten state increases and the moldability tends to decrease. On the other hand, if Mw / Mn is excessively large, the melt viscosity tends to increase and molding becomes difficult.

  The amount of terminal hydroxy groups of the polycarbonate resin is preferably 100 ppm by mass or more, more preferably 200 ppm by mass or more, and still more preferably 400 ppm by mass from the viewpoints of thermal stability, hydrolysis stability, color tone, and the like. As mentioned above, Most preferably, it is 500 mass ppm or more. However, it is usually 1,500 mass ppm or less, preferably 1,300 mass ppm or less, more preferably 1,200 mass ppm or less, and most preferably 1,000 mass ppm or less. When the amount of terminal hydroxy groups of the polycarbonate resin is too small, the laser transmittance tends to be lowered, and the initial hue at the time of molding may be deteriorated. When the amount of terminal hydroxy groups is excessively large, the residence heat stability and the moist heat resistance tend to decrease.

  The production method of the polycarbonate resin is not particularly limited, and a polycarbonate resin produced by any of the phosgene method (interfacial polymerization method) and the melt polymerization method (transesterification method) can be used. Among these, as the polycarbonate resin, a polycarbonate resin produced by a melt polymerization method is preferable from the viewpoint of laser weldability.

  In the melt polymerization method, an ester exchange reaction between an aromatic dihydroxy compound and a carbonic acid diester is performed.

The aromatic dihydroxy compound is as described above.
On the other hand, examples of the carbonic acid diester include dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, and di-tert-butyl carbonate; diphenyl carbonate; substituted diphenyl carbonate such as ditolyl carbonate; Among these, diaryl carbonate is preferable, and diphenyl carbonate is particularly preferable. In addition, 1 type may be used for carbonic acid diester, and it may use 2 or more types together by arbitrary combinations and a ratio.

  The ratio of the aromatic dihydroxy compound and the carbonic acid diester is arbitrary as long as the desired polycarbonate resin can be obtained, but it is preferable to use an equimolar amount or more of the carbonic acid diester with respect to 1 mol of the dihydroxy compound. More preferably, it is used. The upper limit is usually 1.30 mol or less. By setting it as such a range, the amount of terminal hydroxy groups can be adjusted to a suitable range.

  In the polycarbonate resin, the amount of terminal hydroxy groups tends to have a great influence on thermal stability, hydrolysis stability, color tone and the like. For this reason, you may adjust the amount of terminal hydroxy groups as needed by arbitrary well-known methods. In the transesterification reaction, a polycarbonate resin in which the amount of terminal hydroxy groups is adjusted can be usually obtained by adjusting the mixing ratio of the carbonic acid diester and the dihydroxy compound, the degree of vacuum during the transesterification reaction, and the like. In addition, the molecular weight of the polycarbonate resin usually obtained can also be adjusted by this operation.

When adjusting the amount of terminal hydroxy groups by adjusting the mixing ratio of the carbonic acid diester and the aromatic dihydroxy compound, the mixing ratio is as described above.
Further, as a more aggressive adjustment method, there may be mentioned a method in which a terminal terminator is mixed separately during the reaction. Examples of the terminal terminator at this time include monohydric phenols, monovalent carboxylic acids, carbonic acid diesters, and the like. In addition, 1 type may be used for a terminal terminator and it may use 2 or more types together by arbitrary combinations and a ratio.

  When producing a polycarbonate resin by the melt polymerization method, a transesterification catalyst is usually used. Any transesterification catalyst can be used. Among these, it is preferable to use an alkali metal compound and / or an alkaline earth metal compound. In addition, auxiliary compounds such as basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds may be used in combination. In addition, 1 type may be used for a transesterification catalyst and it may use 2 or more types together by arbitrary combinations and a ratio.

  In the melt polymerization method, the reaction temperature is usually 100 to 320 ° C. The pressure during the reaction is usually a reduced pressure condition of 2 mmHg or less (267 Pa or less). As a specific operation, a melt polycondensation reaction may be performed under the conditions in this range while removing by-products such as hydroxy compounds.

  The melt polycondensation reaction can be performed by either a batch method or a continuous method. In the case of a batch system, the order of mixing the reaction substrate, reaction medium, catalyst, additive, etc. is arbitrary as long as the desired polycarbonate resin is obtained, and an appropriate order may be set arbitrarily. However, in view of the stability of the polycarbonate resin and the polycarbonate resin composition, the melt polycondensation reaction is preferably carried out continuously.

In the melt polymerization method, a catalyst deactivator may be used as necessary. As the catalyst deactivator, a compound that neutralizes the transesterification catalyst can be arbitrarily used. Examples thereof include sulfur-containing acidic compounds and derivatives thereof. In addition, a catalyst deactivator may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.
The amount of the catalyst deactivator used is usually 0.5 equivalents or more, preferably 1 equivalent or more, and usually 10 equivalents or less, relative to the alkali metal or alkaline earth metal contained in the transesterification catalyst. Preferably it is 5 equivalents or less. Furthermore, it is 1 mass ppm or more normally with respect to polycarbonate resin, and is 100 mass ppm or less normally, Preferably it is 20 mass ppm or less.

  When the polyester-based resin (b) contains a polybutylene terephthalate resin and a polycarbonate resin, the content of the polybutylene terephthalate resin and the polycarbonate resin is preferably 100 to 50% by weight. It is mass%, More preferably, it is 15-45 mass%, More preferably, it is 20-40 mass%. If the content of the polycarbonate resin is less than 10% by mass, the laser welding strength tends to decrease, and if it exceeds 50% by mass, the moldability may be remarkably decreased.

As the polyester resin (b), it is also preferable from the viewpoint of laser weldability to contain a polybutylene terephthalate resin, polystyrene and / or butadiene rubber-containing polystyrene, and a polycarbonate resin.
The polycarbonate resin is as described above.
Polystyrene is a copolymer of styrene homopolymer or other aromatic vinyl monomer such as α-methylstyrene, paramethylstyrene, vinyltoluene, vinylxylene, etc. within a range of, for example, 50% by mass or less. May be.

The butadiene rubber-containing polystyrene is a copolymerized or blended butadiene rubber component, and the amount of the butadiene rubber component is usually 1% by mass or more and less than 50% by mass, preferably 3 to 40% by mass, more Preferably it is 5-30 mass%, More preferably, it is 5-20 mass%. Polystyrene containing an acrylic rubber component is also conceivable as the rubber component, but polystyrene containing a butadiene rubber component is more preferred because it is poor in toughness. High impact polystyrene (HIPS) is particularly preferable as the butadiene rubber-containing polystyrene.
Among polystyrene or butadiene rubber-containing polystyrene, butadiene rubber-containing polystyrene is preferable, and high impact polystyrene (HIPS) is particularly preferable.

  The polystyrene or butadiene rubber-containing polystyrene preferably has a mass average molecular weight of 50,000 to 500,000, more preferably 100,000 to 400,000, and particularly preferably 150,000 to 300,000. If the molecular weight is less than 50,000, bleeding out is observed in the molded product, or decomposition gas is generated during molding, and it is difficult to obtain sufficient weld strength. If the molecular weight is greater than 500,000, sufficient fluidity is obtained. It is difficult to improve the laser fusion strength.

The polystyrene or butadiene rubber-containing polystyrene preferably has a melt flow rate (MFR) measured at 200 ° C. and 98 N of 0.1 to 50 g / 10 minutes, and preferably 0.5 to 30 g / 10 minutes. More preferably, it is 1-20 g / 10min. If the MFR is smaller than 0.1 g / 10 min, the compatibility with the polyester resin becomes insufficient, and the appearance of delamination may occur during injection molding. On the other hand, if the MFR is larger than 50 g / 10 min, the impact resistance is greatly lowered, which is not preferable.
In particular, in the case of polystyrene, the MFR is preferably 1 to 50 g / 10 minutes, more preferably 3 to 35 g / 10 minutes, and further preferably 5 to 20 g / 10 minutes. In the case of butadiene rubber-containing polystyrene, the MFR is preferably 0.1 to 40 g / 10 minutes, more preferably 0.5 to 30 g / 10 minutes, and 1 to 20 g / 10 minutes. Further preferred.

When the polyester resin (b) includes a polybutylene terephthalate resin, polystyrene and / or butadiene rubber-containing polystyrene and a polycarbonate resin, the resulting polyester resin composition (B) has a crystallization temperature (Tc) of 190 ° C. or lower. It is preferable that That is, laser transmissivity can be further improved by appropriately suppressing the transesterification reaction between the polybutylene terephthalate resin and the polycarbonate resin and appropriately reducing the crystallization temperature. The crystallization temperature (Tc) is more preferably 188 ° C. or less, further preferably 185 ° C. or less, particularly preferably 182 ° C. or less, and most preferably 180 ° C. or less. Moreover, the minimum is 160 degreeC normally, Preferably it is 165 degreeC or more.
The crystallization temperature (Tc) is measured by differential scanning calorimetry (DSC). Specifically, using a differential scanning calorimetry (DSC) machine, the temperature was increased from 30 to 300 ° C. at a rate of temperature increase of 20 ° C./min, held at 300 ° C. for 3 minutes, and then at a temperature decrease rate of 20 ° C./min. It is measured as the peak top temperature of the exothermic peak observed when the temperature is lowered.

The content in the case of including a polybutylene terephthalate resin, polystyrene and / or butadiene rubber-containing polystyrene, and a polycarbonate resin as the polyester resin (b) is as follows.
The content of the polybutylene terephthalate resin is preferably 30 to 90% by mass, and 40 to 80% by mass based on a total of 100% by mass of the polybutylene terephthalate resin, polystyrene and / or butadiene rubber-containing polystyrene and polycarbonate resin. More preferred is 50 to 70% by mass. When the content is less than 30% by mass, the heat resistance may be lowered, and when it exceeds 90% by mass, the transmittance tends to be lowered, which is not preferable.

  The content of polystyrene and / or butadiene rubber-containing polystyrene is preferably 1 to 50% by mass based on a total of 100% by mass of the polybutylene terephthalate resin, polystyrene and / or butadiene rubber-containing polystyrene and polycarbonate resin. 45 mass% is more preferable, and 5-40 mass% is further more preferable. If the content is less than 1% by mass, the laser weldability and toughness may be poor, and if it exceeds 50% by mass, the heat resistance tends to be greatly reduced, which is not preferable.

  The content of the polycarbonate resin is preferably 1 to 50% by mass, more preferably 3 to 45% by mass based on a total of 100% by mass of the polybutylene terephthalate resin, polystyrene and / or butadiene rubber-containing polystyrene and polycarbonate resin. 5 to 40% by mass is more preferable. When the content is less than 1% by mass, the laser weldability is lowered, or the polystyrene and / or butadiene rubber-containing polystyrene is poorly dispersed, and the surface appearance of the molded product is likely to be lowered. If it exceeds 50% by mass, the transesterification with the polybutylene terephthalate resin proceeds and the residence heat stability may decrease, which is not preferable.

  The total content of polystyrene and / or butadiene rubber-containing polystyrene and polycarbonate resin is 10 to 55% by mass in a total of 100% by mass of polybutylene terephthalate resin, polystyrene and / or butadiene rubber-containing polystyrene and polycarbonate resin. It is preferably 20 to 50% by mass, more preferably 25 to 45% by mass. By setting it as such content, it becomes the tendency which is excellent in the balance of heat resistance and laser transmittance, and is preferable.

  Furthermore, the content ratio of the polystyrene and / or butadiene rubber-containing polystyrene and the polycarbonate resin component is preferably 5: 1 to 1: 5, more preferably 4: 1 to 1: 4, in terms of mass ratio. By setting it as such a content rate, it exists in the tendency which is excellent in the balance of heat resistance and a laser transmittance, and is preferable.

The polyester resin (b) preferably contains a polybutylene terephthalate resin and polystyrene and / or butadiene rubber-containing polystyrene from the viewpoint of laser weldability.
The polystyrene and / or butadiene rubber-containing polystyrene is as described above.
When polybutylene terephthalate resin and polystyrene and / or butadiene rubber-containing polystyrene are contained, the content of the polybutylene terephthalate resin and polystyrene and / or butadiene rubber-containing polystyrene is 100% by mass with respect to polystyrene and / or. The butadiene rubber-containing polystyrene is preferably 10 to 50% by mass, more preferably 15 to 45% by mass, and still more preferably 20 to 40% by mass. When the content of polystyrene and / or butadiene rubber-containing polystyrene is less than 10% by mass, the laser welding strength tends to decrease, and when it exceeds 50% by mass, delamination may occur during molding, which may cause poor appearance. Absent.

The polyester resin composition (B) may be imparted with its laser light absorption characteristics by adding a light absorber such as a color pigment. Examples of the color pigment include black pigments such as carbon black, red pigments such as iron oxide red, white pigments such as titanium oxide, and various organic pigments. Among these, inorganic pigments generally have a strong hiding power and can be preferably used. These light absorbers may be used in combination of two or more.
It is preferable that content of a light absorber is 0.01-3 mass parts with respect to 100 mass parts of polyester-type resin (b), 0.05-2 mass parts is more preferable, 0.1-1 mass Part is more preferred.

It is also preferable to contain a laser light absorbing dye having an absorption wavelength within the range of the laser light wavelength to be irradiated.
As the laser light absorbing dye, nigrosine, aniline black, phthalocyanine, naphthalocyanine, porphyrin, perylene, quaterylene, azo dye, anthraquinone, squaric acid derivative, immonium and the like are used.

Of these, a particularly preferred laser-absorbing dye is nigrosine. Nigrosine is C.I. I. SOLVENT BLACK 5 and C.I. I. It is a black azine-based condensation mixture as described in COLOR INDEX as SOLVEN BLACK 7. This can be synthesized, for example, by oxidizing and dehydrating aniline, aniline hydrochloride and nitrobenzene at a reaction temperature of 160 to 180 ° C. in the presence of iron chloride.
Examples of commercially available nigrosine include “NUBIAN (registered trademark) BLACK” (trade name, manufactured by Orient Chemical Industry Co., Ltd.).

  The content of the laser light absorbing dye is preferably 0.001 to 2 parts by mass, more preferably 0.003 to 1.5 parts by mass, and still more preferably 100 parts by mass of the polyester resin (b). Is 0.005 to 1 part by mass.

  Moreover, you may contain together the other absorptive dye with respect to a laser beam, and above-described light absorber. By containing other absorptive dyes and light absorbers, it is also possible to adjust the absorbance of the resin composition for laser welding. As the light absorber, carbon black is particularly preferable.

The polyester resin composition (B) preferably contains a stabilizer.
Examples of the stabilizer include various stabilizers such as a phosphorus stabilizer, a phenol stabilizer, and a sulfur stabilizer. Particularly preferred are hindered phenol stabilizers and phosphorus stabilizers.

  Examples of the hindered phenol stabilizer include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl). -4-hydroxyphenyl) propionate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N'-hexane-1,6-diylbis [3- (3 , 5-di-tert-butyl-4-hydroxyphenylpropionamide), 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphoate, 3,3 ', 3 ", 5,5', 5" -hexa-ter -Butyl-a, a ', a "-(mesitylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3 5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert -Butyl-4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamino) phenol, 2- [1- (2-hydroxy-3,5-di-tert-pentyl) Yl) ethyl] -4,6-di -tert- pentylphenyl acrylate.

  Of these, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate are preferable. . Specific examples of such a phenol-based stabilizer include, for example, trade names (hereinafter the same) “Irganox 1010” and “Irganox 1076” manufactured by BASF, “ADEKA STAB AO-50” manufactured by ADEKA, “ Adekastab AO-60 "etc. are mentioned.

  The content of the hindered phenol stabilizer is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and preferably 1 part by mass with respect to 100 parts by mass of the polyester resin (b). Part or less, more preferably 0.8 part by weight or less, and still more preferably 0.6 part by weight or less.

Examples of phosphorus stabilizers include phosphorous acid, phosphoric acid, phosphite esters, and phosphate esters. Among them, organic phosphate compounds, organic phosphite compounds, or organic phosphonite compounds are preferable, and organic phosphate compounds are particularly preferable. .
As the organic phosphate compound, a compound represented by the following general formula (1) is preferable.

(In General Formula (1), R ¹ represents an alkyl group or an aryl group. N represents an integer of 0 to 2. When n is 0, two R ^{1 s} may be the same or different, When n is 1, two R ¹ may be the same or different.)

In the general formula (1), R ¹ represents an alkyl group or an aryl group. R ¹ is preferably an alkyl group having 1 or more, preferably 2 or more, and usually 30 or less, preferably 25 or less, or an aryl group having 6 or more and usually 30 or less carbon atoms. , R ¹ is preferably an alkyl group rather than an aryl group. In addition, when two or more R ¹ exists, R ¹ may be the same or different from each other.

More preferred is a long-chain alkyl acid phosphate compound in which R ₁ has 8 to 30 carbon atoms than the phosphorus system represented by the general formula (1). Specific examples of the alkyl group having 8 to 30 carbon atoms include octyl group, 2-ethylhexyl group, isooctyl group, nonyl group, isononyl group, decyl group, isodecyl group, dodecyl group, tridecyl group, isotridecyl group, tetradecyl group, A hexadecyl group, an octadecyl group, an eicosyl group, a triacontyl group, etc. are mentioned.

Examples of the long-chain alkyl acid phosphate include octyl acid phosphate, 2-ethylhexyl acid phosphate, decyl acid phosphate, lauryl acid phosphate, octadecyl acid phosphate, oleyl acid phosphate, behenyl acid phosphate, phenyl acid phosphate, nonyl phenyl acid phosphate Acid phosphate, phenoxyethyl acid phosphate, alkoxy polyethylene glycol acid phosphate, bisphenol A acid phosphate, dimethyl acid phosphate, diethyl acid phosphate, dipropyl acid phosphate, diisopropyl acid phosphate, dibutyl acid phosphate, geo Chill acid phosphate, di-2-ethylhexyl acid phosphate, dioctyl acid phosphate, dilauryl acid phosphate, distearyl acid phosphate, diphenyl acid phosphate, and a bis-nonylphenyl acid phosphate, or the like.
Among these, octadecyl acid phosphate is preferable, and this is marketed under the trade name “Adeka Stab AX-71” manufactured by ADEKA.

  The content of the phosphorus stabilizer represented by the general formula (1) is preferably 0.001 to 1 part by mass with respect to 100 parts by mass of the polyester resin (b). When the content is less than 0.001 part by mass, it is difficult to expect improvement in the thermal stability and compatibility of the welding member, and when the amount exceeds 1 part by mass, a decrease in molecular weight and a deterioration in hue are likely to occur. There is an excess amount, silver generation and hue deterioration are more likely to occur, and at the same time, the laser transmittance tends to decrease. A more preferable content is 0.01 to 0.6 parts by mass, and still more preferably 0.05 to 0.4 parts by mass.

  The polyester resin composition (B) preferably further contains a release agent. As the mold release agent, known mold release agents usually used for polyester resins can be used. Among them, one or more mold release agents selected from polyolefin compounds, fatty acid ester compounds, and silicone compounds are used. preferable.

  Examples of the polyolefin compound include compounds selected from paraffin wax and polyethylene wax. Among them, those having a mass average molecular weight of 700 to 10,000, more preferably 900 to 8,000 are preferable. In addition, modified polyolefin compounds in which a hydroxyl group, a carboxyl group, a hydroxyl group, an epoxy group, or the like is introduced into the side chain are also particularly preferable.

  Examples of the fatty acid ester compounds include fatty acid esters such as glycerin fatty acid esters, sorbitan fatty acid esters, pentaerythritol fatty acid esters, and partially saponified products thereof. Among them, carbon atoms are 11 to 28, preferably carbon atoms. Mono- or di-fatty acid esters composed of fatty acids of several 17 to 21 are preferred. Specific examples include glycerol monostearate, glycerol monobehenate, glycerol dibehenate, glycerol-12-hydroxy monostearate, sorbitan monobehenate, pentaerythritol distearate, pentaerythritol tetrastearate and the like.

  Moreover, as a silicone type compound, the compound modified | denatured from points, such as compatibility with resin, is preferable. Examples of the modified silicone oil include silicone oil in which an organic group is introduced into the side chain of polysiloxane, silicone oil in which an organic group is introduced into both ends and / or one end of polysiloxane, and the like. Examples of the organic group to be introduced include an epoxy group, an amino group, a carboxyl group, a carbinol group, a methacryl group, a mercapto group, and a phenol group, and preferably an epoxy group. As the modified silicone oil, a silicone oil in which an epoxy group is introduced into the side chain of polysiloxane is particularly preferable.

  It is preferable that content of a mold release agent is 0.05-2 mass parts with respect to 100 mass parts of polyester-type resin (b). If the amount is less than 0.05 parts by mass, the surface property tends to decrease due to defective mold release at the time of melt molding. On the other hand, if it exceeds 2 parts by mass, the kneading workability of the resin composition decreases, and molding is also performed. The surface of the product may be cloudy. The content of the release agent is preferably 0.07 to 1.5 parts by mass, more preferably 0.1 to 1.0 parts by mass.

It is also preferable that the polyester resin composition (B) further contains a reinforcing filler.
As the reinforcing filler, a conventional inorganic filler for plastics can be used. Preferably, fibrous fillers such as glass fiber, carbon fiber, basalt fiber, wollastonite and potassium titanate fiber can be used. In addition, granular or amorphous fillers such as calcium carbonate, titanium oxide, feldspar minerals, clays, organic clays, glass beads; plate-like fillers such as talc; scale-like fillers such as glass flakes, mica and graphite A material can also be used.
Among these, it is preferable to use glass fiber from the viewpoints of laser light transmittance, mechanical strength, rigidity, and heat resistance.

  More preferably, the reinforcing filler is surface-treated with a surface treatment agent such as a coupling agent. The glass fiber to which the surface treatment agent is attached is preferable because it is excellent in durability, heat and humidity resistance, hydrolysis resistance, and heat shock resistance.

As the surface treatment agent, any conventionally known one can be used. Specifically, for example, silane coupling agents such as amino silane, epoxy silane, allyl silane, and vinyl silane are preferable.
Among these, aminosilane-based surface treatment agents are preferable, and specifically, for example, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, and γ- (2-aminoethyl) aminopropyltrimethoxysilane are preferable. Take as an example.

Moreover, as a surface treating agent, epoxy resins, such as a novolac type, a bisphenol A type epoxy resin, etc. are mentioned preferably. Of these, bisphenol A type epoxy resins are preferred.
The silane-based surface treatment agent and the epoxy resin may be used alone or in combination, and it is also preferable to use both in combination.

From the viewpoint of laser weldability, the glass fiber is also preferably a glass fiber having an anisotropic cross-sectional shape in which the ratio of the major axis to the minor axis is 1.5 to 10.
The cross-sectional shape is preferably an oval, elliptical, or eyebrow-shaped cross section, and particularly preferably an oval cross section. Further, those having a major axis / minor axis ratio of 2.5 to 8, more preferably 3 to 6 are preferred. Furthermore, when the major axis of the cross section of the glass fiber in the molded product is D2, the minor axis is D1, and the average fiber length is L, the aspect ratio ((L × 2) / (D2 + D1)) is preferably 10 or more. When such a flat glass fiber is used, warping of the molded product is suppressed, which is particularly effective when a box-shaped welded body is manufactured.

  Content of a reinforcement filler is 0-100 mass parts with respect to 100 mass parts of polyester-type resin (b). When the content of the reinforcing filler exceeds 100 parts by mass, the fluidity and laser weldability are deteriorated, which is not preferable. The more preferable content of the reinforcing filler is 5 to 90 parts by mass, more preferably 15 to 80 parts by mass, further preferably 30 to 70 parts by mass, and particularly 35 to 60 parts by mass.

The polyester resin composition (B) may contain other additives other than those described above or other thermoplastic resins.
Examples of other additives include flame retardants, flame retardant aids, anti-dripping agents, ultraviolet absorbers, antistatic agents, antifogging agents, lubricants, antiblocking agents, plasticizers, dispersants, and antibacterial agents.
Examples of other thermoplastic resins include polyamide resins, polyphenylene oxide resins, polyphenylene sulfide resins, polysulfone resins, polyether sulfone resins, polyether imide resins, polyether ketone resins, and fluorine resins. The proportion of the other thermoplastic resin in the polyester resin (b) is preferably 20% by mass or less, and more preferably 10% by mass or less.

As a manufacturing method of a polyester resin composition (B), it can carry out in accordance with the conventional method of resin composition preparation. Usually, the components and various additives added as desired are mixed together and then melt-kneaded in a single-screw or twin-screw extruder. Moreover, it is also possible to prepare the resin composition of the present invention by 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.
In addition, when using fibrous reinforcement fillers, such as glass fiber, it is also preferable to supply from the side feeder in the middle of the cylinder of an extruder.

  The heating temperature at the time of melt kneading can be appropriately selected from the range of usually 220 to 300 ° C. If the temperature is too high, decomposition gas is likely to be generated, which may cause opacity. Therefore, it is desirable to select a screw configuration in consideration of shear heat generation.

  The second member can be produced by arbitrarily adopting the above-described polyester resin composition (B) by a molding method generally employed for the polyester resin composition. For example, injection molding method, ultra-high speed injection molding method, injection compression molding method, two-color molding method, hollow molding method such as gas assist, molding method using heat insulating mold, rapid heating mold were used. Molding method, foam molding (including supercritical fluid), insert molding, IMC (in-mold coating molding) molding method, extrusion molding method, sheet molding method, thermoforming method, rotational molding method, laminate molding method, press molding method, Examples thereof include a blow molding method. Of these, injection molding is preferred. As the injection molding method, for example, a high-speed injection molding method, an injection compression molding method, or the like can be used.

  The shape of the second member is not particularly limited, but since the members are joined and used by laser welding, it is usually preferable to have a shape having at least a surface-contactable portion, for example, a flat surface portion or a curved surface portion.

[First member]
The first member, which is the counterpart material of the second member described above, is a laminate formed by laminating a layer made of polyester resin (A) on the metal substrate as the outermost layer.

  Examples of the metal of the metal substrate in the first member include various metals such as aluminum, iron, copper, tin, nickel, and zinc. Among these, aluminum and iron are preferable, and aluminum is more preferable. Examples of aluminum include pure Al and various Al alloys. Examples of iron include iron such as iron, steel, and stainless steel, and various iron alloys.

Although there is no restriction | limiting in particular as a shape of a metal base | substrate, A plate shape, a sheet form, a film etc. are mentioned preferably.
The thickness of the metal substrate is preferably in the range of 0.05 to 10 mm, more preferably 0.1 to 5 mm, and further preferably 0.2 to 2 mm. The thickness in the case of an aluminum plate or an iron plate is preferably from 0.1 to 3 mm, and preferably from 0.2 to 2.5 mm.

  The metal substrate is preferably subjected to chemical conversion treatment or various surface treatments. By performing such a treatment, the adhesion (adhesiveness or adhesive strength) between the metal substrate and the resin layer can be improved.

  As a preferable chemical conversion treatment in the case of an aluminum substrate, chemical conversion treatment with phosphoric acid chromate or the like, anodic oxidation treatment and the like can be mentioned.

Although the thickness of the thin film formed by the said chemical conversion treatment is not specifically limited, 5-300 nm is good. When the thickness of the chemical conversion treatment thin film is less than 5 nm, workability may be inferior, and when it exceeds 300 nm, formation of the thin film may be difficult.
Moreover, when a chemical conversion treatment thin film is an anodized thin film, the range of 0.05-2 micrometers is preferable and the range of 0.1-2 micrometers is more preferable. If the thickness of the anodic oxide coating is less than 0.05 μm, the adhesion may not be improved. The thickness of the anodic oxide coating can be adjusted to a thickness within the above range by adjusting the processing conditions, particularly the energizing conditions and energizing time.

  Examples of the anodizing treatment include a treatment thin film using phosphoric acid, phosphoric acid-sulfuric acid, phosphoric acid-oxalic acid, phosphoric acid-chromic acid as an electrolytic solution. Among these, it is preferable to use an alumite phosphate treatment.

Examples of the treatment of the surface of the metal substrate include a method of performing single layer plating, multilayer plating or alloy plating, immersion chromic acid treatment or phosphoric acid chromic acid treatment in addition to the chemical conversion treatment. Either electroplating or electroless plating may be used, but particularly when the metal substrate is iron, zinc, tin, nickel, and copper plating are preferable, and galvanization is more preferable.
In addition, by applying electrolytic chromic acid treatment, the surface of the metal plate is a single-layer film made of chromium hydrated oxide, or a two-layer film made of a metal chromium layer (lower layer) and a chromium hydrated oxide layer (upper layer). It is also preferable to form

It is preferable that a metal substrate, particularly an aluminum substrate and an iron substrate, to which the above-described surface treatment is preferably applied, be surface-treated with a silane coupling agent.
Although it does not specifically limit as a silane coupling agent, For example, the compound which has a methoxy group, an ethoxy group, a silanol group etc. is mentioned, As a silane coupling agent, vinyl trimethoxysilane, chloropropyltrimethoxysilane, 3-glycol is mentioned. Sidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-aminoethyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- ( N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane hydrochloride, ureidoaminopropylethoxysilane and the like are preferred. In particular, an aluminum substrate, an iron substrate, and a silane coupling agent form a bond of Al—O—Si or Fe—O—Si, and are firmly bonded. In addition, the polyester resin (A) is an organic compound of a silane coupling agent. A functional group reacts and bonds firmly, and a stronger bond can be achieved.

Furthermore, it is preferable to provide an adhesive layer on the metal substrate regardless of the presence or absence of the chemical conversion treatment or the silane coupling agent treatment.
As the adhesive, it is preferable to use an acrylic adhesive, an epoxy adhesive, a urethane adhesive, a polyester adhesive, or the like. Among these, in the case of a laminate comprising a combination of an aluminum substrate, an iron substrate and a polyester resin (A), it is particularly preferable to use a thermosetting polyester adhesive.

  The metal substrate is preferably provided with the above-mentioned chemical conversion treatment, silane coupling agent treatment, and further an adhesive layer, and a layer made of polyester resin (A) is formed as the outermost layer. The polyester resin (A) layer is preferably subjected to surface treatment such as corona treatment or flame treatment for the purpose of improving adhesion.

  As this polyester resin (A), the thing similar to the above-mentioned polyester-type resin (b) which comprises the polyester resin composition (B) of a 2nd member can be used. Among them, polybutylene terephthalate resin, polybutylene isophthalate resin, polytrimethylene terephthalate resin, polyethylene terephthalate resin, poly-1,4-cyclohexadimethylene terephthalate resin, copolymerized polyester resins thereof, and mixtures thereof are preferable. Can be mentioned.

The intrinsic viscosity of the polyester resin (A) is preferably 0.5 to 2 dl / g, and preferably has an intrinsic viscosity in the range of 0.6 to 1.5 dl / g.
The intrinsic viscosity of the polyester resin (A) is a value measured at 30 ° C. in a 1: 1 (mass ratio) mixed solvent of tetrachloroethane and phenol.

  The polyester resin (A) can be blended with various resin additives and other resins as necessary, and various components that can be contained in the polyester resin composition (B) are used in the same manner. it can.

  The method for providing the layer made of the polyester resin (A) on the metal substrate is not particularly limited. Extrusion molding using a coat hanger die, T-die, I-die, inflation die, etc., calendar molding It can be produced by a conventionally known method such as a method, and a polyester resin (A) film that has been formed may be laminated. In the lamination, for example, a polyester resin (A) film may be pressure-laminated by a nip roll or the like heated below the melting point of the polyester resin (A). And after laminating, it cools by air cooling or water cooling immediately. The polyester resin (A) film may be unstretched or biaxially stretched.

  As described above, the polyester resin (A) layer may be provided directly on the metal substrate. However, the polyester resin (A) layer is formed via any one or more of a chemical conversion treatment layer, a silane coupling agent treatment layer, and an adhesive layer. It is preferable.

  The thickness of the polyester resin (A) layer is preferably 3 to 1000 μm, more preferably 5 to 800 μm, further preferably 5 to 600 μm, and particularly preferably in the range of 10 to 400 μm.

  Moreover, the polyester resin (A) layer may have a multilayer structure. In this case, it is preferable to first laminate only the first polyester resin layer on the metal substrate. In the method of laminating and integrating a plurality of polyester resin layers and then laminating on a metal substrate, wrinkles are likely to occur on the surface, and the surface properties may be deteriorated.

  The method of forming the polyester resin layer after the first polyester resin layer is laminated on the metal substrate is not particularly limited, but is preferably laminated after applying various adhesives. As the adhesive, an acrylic adhesive, an epoxy adhesive, a urethane adhesive, a polyester adhesive, various adhesives such as a thermosetting type and an energy ray curable type such as an ultraviolet ray can be applied.

[Laser welding]
The second member made of the polyester resin composition (B) described above is irradiated with laser light on the first member which is a laminate having the layer made of the polyester resin (A) as the outermost layer on the metal substrate. And welded to the layer made of the polyester resin (A).

  For laser welding, i) a method in which the second member is made to be transparent to the laser beam and the laser beam transmitted through the second member is absorbed by the first member and melted to weld both members, ii) There is a method in which the balance of laser light transmission and absorption is adjusted for the second member, the resin is melted by both the second member and the first member, and both the members are welded. It may be.

  In the case of the above method ii), as described above, the polyester resin composition (B) is a light absorber such as carbon black or a laser light absorber such as nigrosine having an absorption wavelength within the range of the laser light wavelength to be irradiated. It is preferable to contain a functional dye.

  The thickness of the portion of the second member that transmits or absorbs the laser can be appropriately determined in consideration of the application, the composition of the composition, and the like, but is, for example, 5 mm or less, preferably 4 mm or less, more preferably It is 3 mm or less, particularly preferably 2 mm or less, and particularly preferably 1.5 mm or less.

  Various types of laser light can be applied and can be appropriately selected. YAG (yttrium, aluminum, garnet crystal) laser (wavelength 1064 nm), LD (laser diode) laser (wavelength 808 nm, 840 nm, 940 nm) Etc. can be preferably used.

  In particular, in the case of the method i), the laser welding part preferably has a light transmittance of 40% or more in laser light having a wavelength of 940 nm, more preferably 45% or more, and even more preferably 50% or more. It is preferably 55% or more, particularly 60% or more, particularly 65% or more, and most preferably 70% or more.

In order to laser weld the second member made of the polyester resin composition (B) to the first member and the outermost layer side of the first member, first, the portions to be welded are brought into contact with each other. At this time, surface contact is desirable between the two welded portions, and may be flat surfaces, curved surfaces, or a combination of flat and curved surfaces. Although it is possible to sandwich an adhesive sheet or the like between the first member and the second member, the present invention does not require such an adhesive sheet or the like, and does not require any strong bonding. Is possible.
Next, laser light is irradiated from the second member side. At this time, the laser beam may be condensed at the interface between the two using a lens system if necessary. The condensed beam passes through the second member, is absorbed near the surface with the first member, generates heat, and melts. Next, the heat is transmitted to both members by heat conduction and melted to form a molten pool at the interface between the two, and after cooling, both are welded. Thus, the resin metal composite in which the polyester resins are welded to each other exhibits high welding strength, and achieves a strong bond that causes the base material to break as shown in the examples.

Further, separately from the above-mentioned methods i) and ii), iii) the first member and the polyester resin part of the second member are brought into contact with each other, preferably in surface contact, and then the laser beam is emitted from the metal substrate side. It has also been found possible to irradiate and heat the metal substrate. Even when the metal substrate is heated by irradiation from the metal substrate side, the polyester resin (A) layer and the polyester resin composition (B) are melted and integrated, and firmly fixed as shown in the examples. Resin-metal composite becomes possible.
In this case, the thickness of the metal substrate in the first member can be appropriately determined in consideration of the use, the thermal conductivity of the metal substrate, the composition of the polyester resin composition (B), etc., but preferably, for example, 10 mm or less. More preferably, it is 8 mm or less, more preferably 5 mm or less, especially 4 mm or less, especially 3 mm or less, particularly 2 mm or less.

The shape, size, thickness, etc. of the resin-metal composite of the present invention integrated by laser welding are arbitrary, and such resin-metal composite has an extremely good degree of adhesion at the interface between both members and has a good sealing property.
Therefore, its use is suitable for various parts, especially electrical parts for transportation equipment such as automobiles that require high antistatic performance (various control units, ignition coil parts, sensor parts, motor parts, etc.) It is suitable for housing cases, covers and the like for electrical and electronic equipment parts.

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated more concretely, this invention is limited to a following example and is not interpreted.

[First member: Production of polyester resin (A) aluminum laminate]
An aluminum plate (JIS A1050) with a thickness of 0.4 mm was anodized with a 20% phosphoric acid solution to form a phosphoric acid alumite-treated film with a thickness of 0.5 μm. On this coating, 20 mg / m ² of a silane coupling agent was applied, and the coated surface was heated to 250 ° C. Further, after applying a thermosetting polyester-based adhesive and drying by heating, polybutylene terephthalate resin (manufactured by Mitsubishi Engineering Plastics, trade name “Novaduran (registered trademark) 5020S”, intrinsic viscosity: 1.24 dl / g, melting point: 224 ° C., glass transition temperature: 80 ° C.) A 150 μm thick film produced separately by an extruder is stacked and pressed by a pair of pressure rolls to laminate a polyester resin aluminum laminate for the second member. Obtained.

  Further, for comparison, a stainless steel plate (SUS304, thickness: 0.4 mm) and an aluminum plate (A2017, thickness: 0.4 mm) without a polyester resin (A) coating were separately prepared.

(Second member: Production of polyester resin composition)
As a raw material component of the polyester resin composition (B) used for the second member, the components described in Table 1 below were used.

Among the components described in Table 1 above, blended in amounts (all parts by mass) described as the resin compositions a to l in Table 2 below, this was blended with a 30 mm vent type twin screw extruder (Nippon Steel Works). Glass fiber is supplied from a side feeder, melt-kneaded at a barrel temperature of 270 ° C., extruded into a strand shape, pelletized by a strand cutter, and resin compositions a to l A pellet of the polybutylene terephthalate resin composition was obtained.
The obtained polybutylene terephthalate resin composition pellets of the above resin compositions a to l were dried at 120 ° C. for 5 hours, and then cylinder temperature 250 with an injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd., model: NEX80-9E). An ASTM No. 4 dumbbell piece (thickness 1 mm) for laser welding evaluation second member shown in FIG. 1 was manufactured by injection molding under the conditions of ℃ and mold temperature of 80 ℃. In addition, 1 in FIG. 1 shows the gate position at the time of injection molding, 2 shows the laser irradiation location in the laser welding evaluation mentioned later.

About the laser welding part (refer FIG. 1) of the anti-gate part of the ASTM No. 4 dumbbell piece for the second member obtained above, transmission at a wavelength of 940 nm using a spectrophotometer (“UV-3100PC” manufactured by Shimadzu Corporation) The rate (unit:%) was determined.
The results are listed in Table 2 below.

(Examples 1-12)
On the polyester resin layer of the said 1st member, the 2nd member of the resin composition of said a-1 was piled up, and the laser was irradiated from the polyester resin composition (B) side of the 2nd member.

  Laser welding uses a fine device laser device (laser 140W, fiber core diameter 0.6 mm), laser wavelength: 940 nm, laser scan speed: 2 mm / second, scan length: 10 mm, laser output: 140 W, pressure: 0 The distance between the laser head and the second member was 79.7 mm.

  Moreover, the said 2nd member was piled up on the polyester resin layer of the said 1st member, and the same laser irradiation was performed by the inclination of 2 degrees from the aluminum base | substrate side of the 1st member.

Laser welding strength was measured using the welded resin metal composite. Weld strength is measured by using a tensile tester (Instron “5544”), and the first and second members integrated by welding are clamped at both ends in the long axis direction. Evaluation was made by pulling at a pulling speed of 5 mm / min. The laser welding strength was evaluated by the tensile shear fracture strength (unit: N) of the welded portion. Further, at this time, when the strength of the welded portion was large and finally caused the base material destruction, it was described as the base material destruction.
The results of the welding test are shown in Table 3 below.

(Comparative Examples 1-2)
In Example 1, laser light irradiation was performed from the polyester resin composition (B) side of the second member in the same manner except that the first member was changed to a stainless steel plate or aluminum plate without the polyester resin coating described above. It was.
Table 3 shows the results of the welding test performed in the same manner as in Example 1.

  As is apparent from the results in Table 3, the laser-welded resin / metal composites of Examples 1 to 10 exhibited high laser weldability until the base material was destroyed. Since the tensile shear fracture strength of the welded part was 600 N in Examples 1 to 10 and 350 N in Examples 11 and 12, the second member was a glass fiber reinforced resin composition (Examples 1 to 10). Has an extremely high welding strength exceeding 600 N, and when the second member is a non-reinforced resin composition (Examples 11 and 12), it is presumed to have a high welding strength exceeding 350 N.

  The laser-welded resin / metal composite of the present invention is remarkably excellent in the adhesion between the polyester resin and the metal substrate, so that it is particularly an electrical component for transport equipment such as automobiles (sensor parts, ECU cases, motor parts, battery parts). It can be suitably used for electrical and electronic equipment parts, industrial machine parts, and other consumer parts.

1: Gate 2: Laser irradiation location

Claims (9)

  It is characterized in that a second member made of a polyester resin composition (B) is laser-welded on a first member made by laminating a layer made of a polyester resin (A) on a metal substrate as an outermost layer. Resin metal composite.   The resin metal composite according to claim 1, wherein the metal substrate is made of aluminum or iron.   The said 1st member is a laminated body which laminated | stacked the layer which consists of a polyester resin (A) as an outermost layer through an adhesive layer after performing a chemical conversion treatment on a metal base | substrate. Resin metal composite.   The polyester resin composition (B) includes a polybutylene terephthalate resin and a polyethylene terephthalate resin as the polyester resin (b), and the content of the polyethylene terephthalate resin is 100% by mass in total of the polybutylene terephthalate resin and the polyethylene terephthalate resin. It is 10-50 mass%, The resin metal composite of any one of Claims 1-3.   The polyester resin composition (B) contains a polybutylene terephthalate resin and a modified polybutylene terephthalate resin as the polyester resin (b), and the content of the modified polybutylene terephthalate resin is that of the polybutylene terephthalate resin and the modified polybutylene terephthalate resin. It is 20-70 mass% with respect to 100 mass% in total, The resin metal composite of any one of Claims 1-3.   The polyester resin composition (B) contains a polybutylene terephthalate resin and a polycarbonate resin as the polyester resin (b), and the content of the polycarbonate resin is 10 with respect to a total of 100% by mass of the polybutylene terephthalate resin and the polycarbonate resin. The resin metal composite according to any one of claims 1 to 3, which is -50% by mass.   The polyester resin composition (B) contains, as the polyester resin (b), a polybutylene terephthalate resin, polystyrene and / or butadiene rubber-containing polystyrene and a polycarbonate resin, and a polybutylene terephthalate resin, polystyrene and / or butadiene rubber-containing polystyrene. The polybutylene terephthalate resin is contained in an amount of 30 to 90% by mass, polystyrene and / or butadiene rubber-containing polystyrene is contained in an amount of 1 to 50% by mass, and the polycarbonate resin is contained in an amount of 1 to 50% by mass based on a total of 100% by mass of the polycarbonate resin. The resin metal composite according to any one of -3.   A second member made of the polyester resin composition (B) is laser-beamed from the second member side on the first member formed by laminating the layer made of the polyester resin (A) on the metal substrate as the outermost layer. The manufacturing method of the resin metal composite characterized by irradiating and welding.   A second member made of the polyester resin composition (B) is placed on the metal member side of the first member on the first member formed by laminating the layer made of the polyester resin (A) on the metal substrate as the outermost layer. A method for producing a resin-metal composite comprising irradiating a laser beam and welding.