Anchor coating agent

Abstract

To provide an anchor coating agent which is excellent in production suitability, and forms an anchor coating layer having balanced high adhesion, high metal plating property and high hardness, and a high adhesion laminate having the anchor coating layer manufactured using the anchor coating agent.MEANS FOR SOLVING THE PROBLEM: An anchor coating agent contains specific colloidal silica (A), a silicate binder (B), and a solvent (C), and forms an anchor coating layer between a base material layer and a resin layer or a metal plating layer.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to an anchor coating agent for forming an anchor coating layer (AC layer) having excellent manufacturing suitability, excellent balance of high adhesion, high plating property, and high hardness, a high-adhesion laminate having the anchor coating layer produced using the anchor coating agent, and a metal plating laminate.

Background Art

[0002] In electronic devices and automobiles, electrical components and electronic components using glass, resin, and metal lead frames are used, and the bonding and adhesion between various metals, resins, and metal plating surfaces are required. Patent Documents 1, 2, and 3 disclose attempts to bond metal members with an adhesive resin, but it was necessary to previously perform surface treatment on the metal surface by physical treatment or chemical treatment, or the metal member and the adhesive resin were integrally molded by injection molding or the like, and it was not suitable for bonding or adhering small parts.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0004] An object of the present invention is to provide an anchor coating agent for forming an anchor coating layer having excellent manufacturing suitability, excellent balance of high adhesion, high metal plating property, and high hardness, a high-adhesion laminate having the anchor coating layer produced using the anchor coating agent, and a metal plating laminate.

Means for Solving the Problems

[0005] As a result of various studies, the inventors of the present invention have found that an anchor coating agent containing at least a specific colloidal silica (A), a specific silicate binder (B), and a solvent (C) achieves the above problems.

[0006] That is, the present invention is characterized by the following points. [1] An anchor coating agent for forming an anchor coating layer between a base material layer and a resin layer or a metal plating layer to enhance the adhesiveness between the base material layer and the resin layer or the metal plating layer, The anchor coating agent contains colloidal silica (A), a silicate binder (B), and a solvent (C), The colloidal silica (A) may contain chain silica and / or pearl necklace-shaped silica, The above-mentioned anchor coating agent. [2] The anchor coating agent according to [1] above, wherein the content of colloidal silica (A) in the solid content of the anchor coating agent is 30% by mass or more and 90% by mass or less. [3] The anchor coating agent according to [1] or [2] above, wherein 60% by mass or more of the colloidal silica (A) is chain silica and / or pearl necklace-shaped silica. [4] The anchor coating agent according to any one of [1] to [3] above, further containing an adhesion promoter (D). [5] A high-adhesion laminate having an anchor coating layer and a resin layer adjacent to each other in this order on a base material layer, The anchor coating layer is a layer made of the anchor coating agent according to any one of [1] to [4] above, The above-mentioned high-adhesion laminate. [6] A metal plating laminate having an anchor coating layer and a metal plating layer adjacent to each other in this order on a base material layer, The anchor coating layer is a layer made of the anchor coating agent described in any one of the above [1] to [4]. The metal plating laminate.

Advantages of the Invention

[0007] The present invention can provide an anchor coating agent for forming an anchor coating layer excellent in production suitability and having an excellent balance of high adhesion, high plating property, and high hardness, a high-adhesion laminate having the anchor coating layer produced using the anchor coating agent, and a metal plating laminate.

Brief Description of the Drawings

[0008]

Figure 1

Figure 2

Embodiments for Carrying Out the Invention

[0009] The anchor coating agent, high-adhesion laminate, and metal plating laminate of the present invention will be described in more detail below. Although the description will be made with specific examples, the present invention is not limited thereto.

[0010] 1. Anchor Coating Agent The anchor coating agent of the present invention is an anchor coating agent for forming an anchor coating layer between a base material layer and a resin layer or a metal plating layer to enhance the adhesiveness between the base material layer and the resin layer or the metal plating layer, and contains colloidal silica (A), a silicate binder (B), and a solvent (C). There is no particular limitation on the coating method of the anchor coating agent of the present invention, and it can be applied by any of spraying, dipping, spin coating, cross coating, etc. The drying and curing temperature is preferably 15°C to 150°C.

[0011] In order to enhance adhesion, the anchor coating agent of the present invention may further contain an adhesion promoter (D). In addition, the anchor coating agent of the present invention may, as necessary, further contain a wetting agent, a viscous material (thickener), a surface conditioning material, a coloring material (pigment, dye), an antistatic material, a conductivity-imparting agent, an antibacterial and antiviral material, various fillers, etc., as long as they do not adversely affect the properties of the anchor coating agent or the high-adhesion laminate.

[0012] By applying, drying, and curing the anchor coating agent of the present invention between two layers to form an anchor coating layer, the adhesive strength between the lower layer and the upper layer adjacent to the anchor coating layer can be enhanced, and the peel resistance of the laminate can be improved. When laminating the upper layer, the anchor coating layer may be in any of an uncured state, a semi-cured state, or a fully cured state, and it is not necessary to laminate the upper layer in an uncured or semi-cured state like an adhesive layer. For example, by applying, drying, and curing the anchor coating agent between a substrate layer and a resin layer to form an anchor coating layer, the adhesive strength between the substrate layer and the resin layer adjacent to the anchor coating layer can be enhanced, and the peel resistance of the laminate can be improved.

[0013] Moreover, the anchor coating agent of the present invention can be used as a metal plating pretreatment agent. Even for a material such as glass that is usually difficult to subject to metal plating treatment, by using the anchor coating agent of the present invention as a metal plating pretreatment agent and forming an anchor coating layer on the glass surface, it becomes possible to form a metal plating layer on the glass.

[0014] Furthermore, the anchor coating agent of the present invention can be used as an antireflection treatment agent, and the anchor coating layer formed from the anchor coating agent of the present invention can be used as an antireflection layer having an antireflection function that exhibits a minimum reflectance and a low light reflectance of 1.0% or less in a wide light wavelength range of 380 nm to 780 nm of the light wavelength. In this usage mode, the anchor coating layer may be a surface layer, and a fouling prevention layer, an antibacterial layer, or the like may be further laminated on the anchor coating layer.

[0015] The anchor coating agent of the present invention contains colloidal silica (A), thereby enhancing the surface hardness and slidability of the anchor coating layer formed from the anchor coating agent, and enhancing the adhesion between the base material layer and the resin layer or the metal plating layer. The content of colloidal silica (A) in the solid content (non-volatile content) of the anchor coating agent is preferably 30% by mass or more and 90% by mass or less, and more preferably 40% by mass or more and 80% by mass or less. If it is less than the above range, the anchor effect tends to be insufficient. If it is more than the above range, the coatability tends to be poor, and the anchor coating layer tends to be brittle.

[0016] The anchor coating agent of the present invention contains a silicate binder (B), thereby coating and connecting colloidal silica (A), enhancing the surface hardness of the anchor coating layer, and enhancing the adhesiveness between the base material layer and the resin layer or the metal plating layer. In addition, the resin of the base material layer and / or the resin layer, or the metal plating enters the uneven shape on the surface of the anchor coating layer formed by colloidal silica (A), and the adhesiveness can be enhanced by increasing the adhesion area and the hook-anchor effect. Furthermore, the functional groups of colloidal silica (A) and / or the silicate binder (B) react with the base material layer and / or the resin layer to bond, thereby enhancing the adhesiveness, and furthermore, the durability such as hydrolysis resistance, heat resistance, and flexibility can also be improved.

[0017] The anchor coating agent of the present invention can be applied to the base material layer and used. The surface of the base material layer may be a paint layer such as an acrylic clear coating film. Examples of materials constituting the base material layer include inorganic materials and / or organic materials. Examples of inorganic materials include metal oxides and metals such as ceramics, glass, stainless steel, copper, aluminum, and Ni plating. As an example of a base material using glass, a glass plate, a glass cloth, etc. can also be used. Examples of organic materials include resins, and specific examples of resins include, but are not limited to, PMMA (polymethyl methacrylate), PC (polycarbonate), PET (polyethylene terephthalate), PP (polypropylene), etc. Among these, PMMA is preferred.

[0018] The thickness of the anchor coating layer formed from the anchor coating agent of the present invention is preferably 50 to 2000 nm, more preferably 100 to 1000 nm. If it is thinner than the above range, the anchor effect is likely to be inferior, and since the coating method is limited to make it thicker than the above range, it is substantially difficult to obtain.

[0019] The surface hardness of the anchor coating layer formed from the anchor coating agent of the present invention is preferably H or more in terms of the surface hardness measured in accordance with JIS K5600-5-4 "Scratch hardness (pencil method)".

[0020] The surface roughness Ra of the anchor coating layer formed from the anchor coating agent of the present invention is preferably 0.5 to 20 nm, more preferably 2 to 10 nm. If the surface roughness Ra is within the above range, it is easy to obtain high adhesion with the upper and lower layers.

[0021] There is no particular limitation on the resin layer formed on the anchor coating layer formed from the anchor coating agent of the present invention, but the resin contained in the resin layer is preferably a thermoplastic resin. Specific examples of thermoplastic resins include, but are not limited to, PP and PET. There is no particular limitation on the thickness of the resin layer, but it is preferably 1 to 100 μm, more preferably 2 to 30 μm.

[0022] <Colloidal silica (A)> Colloidal silica (A) is silica particles in a colloidal state of solid content and is dispersed in a solvent. Also, the mixture of colloidal silica and the solvent is a colloidal silica sol. Colloidal silica (A) is preferably nano silica. The average particle size of colloidal silica (A) is preferably 2 to 500 nm, more preferably 5 to 50 nm, and even more preferably 8 to 20 nm. By using colloidal silica with an average particle size smaller than the above range, secondary aggregation is likely to occur. If the average particle size is larger than the above range, it becomes difficult to balance surface hardness, slidability, and adhesion to the base material layer.

[0023] Colloidal silica (A) preferably contains chain colloidal silica and / or pearl necklace-shaped colloidal silica. When colloidal silica (A) is chain colloidal silica and / or pearl necklace-shaped colloidal silica, the effect of enhancing the surface hardness and adhesion of the anchor coating layer is enhanced. The content of chain colloidal silica and / or pearl necklace-shaped colloidal silica in colloidal silica (A) is preferably 60% by mass or more and 100% by mass or less, and more preferably 70% by mass or more and 95% by mass or less. If it is less than the above range, the effect of enhancing the surface hardness and adhesion of the anchor coating layer is likely to be insufficient. Even if it is more than the above range, the effect of enhancing the surface hardness and adhesion of the anchor coating layer does not improve much.

[0024] <Silicate binder (B)> The silicate binder (B) contains an alkyl silicate and / or an alkyl silicate partially hydrolyzed and condensed oligomer. And the silicate binder (B) may further contain a catalyst as needed. The content rate of the alkyl silicate and / or the alkyl silicate partially hydrolyzed and condensed oligomer in the anchor coating agent is preferably 5 to 30% by mass, and more preferably 10 to 20% by mass.

[0025] [Alkyl silicate, alkyl silicate partially hydrolyzed and condensed oligomer] An alkyl silicate is a silane compound having one or more alkoxys, and may have one or more alkyl groups. Further, the alkyl silicate may be an alkyl silicate having a functional group, an amino group-containing alkyl silicate, or an epoxy group-containing alkyl silicate. The alkyl silicate partially hydrolyzed and condensed oligomer is an oligomer formed by partial hydrolysis and dehydration condensation of the above alkyl silicate (alkoxysilane), and is soluble in a solvent ( C). In the present invention, as the alkyl silicate and / or the alkyl silicate partially hydrolyzed and condensed oligomer, the above compounds can be used alone or in combination of two or more.

[0026] Specific examples of the alkyl silicate include, but are not limited to, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, ethyltriethoxysilane, propyltripropoxysilane, butyltributoxysilane and the like. In the present invention, as the alkyl silicate, the above compounds can be used alone or in combination of two or more.

[0027] Specific examples of the amino group-containing alkyl silicate include, but are not limited to, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyldimethylmethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylethyldiethoxysilane, 3-aminopropyldiethylethoxysilane, 8-aminooctyltrimethoxysilane, and the like. Among these, 3-aminopropyltrimethoxysilane is preferred. In the present invention, as the amino group-containing alkyl silicate, the above compounds can be used alone or in combination of two or more.

[0028] Specific examples of the epoxy group-containing alkyl silicate include, but are not limited to, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylethyldiethoxysilane, 3-glycidoxypropyldiethylethoxysilane, 8-glycidoxyoctyltrimethoxysilane, etc. Among these, 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropylmethyldimethoxysilane are preferred. In the present invention, as the epoxy group-containing alkyl silicate, the above compounds can be used alone or in combination of two or more.

[0029] [Catalyst] The catalyst can promote the hydrolysis reaction and dehydration condensation reaction of the alkyl silicate partial hydrolysis condensation oligomer, alkoxysilane monomer, and colloidal silica (A). Therefore, the catalyst can be used as a catalyst when synthesizing the alkyl silicate partial hydrolysis condensation oligomer in the silicate binder (B) and / or when curing the anchor coating layer formed from the anchor coating agent.

[0030] The content of the catalyst in the silicate binder (B) is preferably 0.05 to 10% by mass, more preferably 0.1 to 5.0% by mass. If it is less than the above range, the effect of promoting the formation of the alkyl silicate partial hydrolysis condensation oligomer tends to be insufficient, and if it is more than the above range, the formation of the alkyl silicate partial hydrolysis condensation oligomer tends to be non-uniform.

[0031] In the anchor coating agent of the present invention, the content of the catalyst is preferably 0.05 to 10% by mass, more preferably 0.1 to 5.0% by mass. If it is less than the above range, the promoting effect of increasing the surface hardness of the anchor coating layer is likely to be insufficient. If it is more than the above range, the surface hardness of the anchor coating layer is likely to be non-uniform.

[0032] As the catalyst, an acid catalyst or a base catalyst can be used. Specific examples of the acid catalyst include, but are not limited to, hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid, benzenesulfonic acid, 10-camphorsulfonic acid, formic acid, oxalic acid, acetic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, lactic acid, etc. Specific examples of the base catalyst include triethylenediamine, dimethylaminoethanol, aqueous ammonia, etc. Among these, nitric acid as the acid catalyst is preferred. In the present invention, as the catalyst, the above compounds can be used alone or in combination of two or more.

[0033] <Solvent (C)> The solvent (C) is not particularly limited as long as it can dissolve or disperse the colloidal silica (A) and the silicate binder (B), but it preferably contains an alcohol-based solvent and / or a glycol-based solvent. In addition, when the anchor coating agent of the present invention is cured at a low temperature, in order to dry it at a low temperature, it is preferable to use a solvent with a low boiling point. When the anchor coating agent of the present invention is dried and cured at, for example, 40°C or lower within 1 hour, it is preferable to use a solvent having 10 or less carbon atoms and a boiling point of 50 to 90°C. Solvents with a lower boiling point than the above range are difficult to handle, and solvents with more carbon atoms and a higher boiling point than the above range will require high temperature and long time for the drying of the anchor coating layer formed from the anchor coating agent. When drying at 80°C or higher, the appearance can be made smoother by using a high-boiling solvent with a boiling point of 120°C to 220°C in combination.

[0034] Specific examples of alcohol solvents include methanol (carbon number 1, boiling point 65°C), ethanol (carbon number 2, boiling point 78°C), normal propanol (carbon number 3, boiling point 97°C), isopropyl alcohol (carbon number 3, boiling point 82°C), tertiary butanol (carbon number 4, boiling point 82°C), normal butanol (carbon number 4, boiling point 118°C), isobutanol (carbon number 4, boiling point 108°C), secondary butanol (carbon number 4, boiling point 100°C), 1-pentanol (carbon number 5, boiling point 138°C), 2-methyl-1-butanol (carbon number 5, boiling point 128°C), 3-methyl-1-butanol (carbon number 5, boiling point 131°C), 2-pentanol (carbon number 5, boiling point 119°C), 1-ethyl-1-propanol (carbon number 5, boiling point 116°C), 2-methyl-2-butanol (carbon number 5, boiling point 102°C), etc., but are not limited thereto. Among these, ethanol and normal butanol are preferred.

[0035] Specific examples of glycol solvents include alkylene glycols and alkylene glycol ethers. Specific alkylene glycols include ethylene glycol (carbon number 2, boiling point 197°C), propylene glycol (carbon number 3, boiling point 189°C), butylene glycol (carbon number 4, boiling point 207°C), hexylene glycol (carbon number 6, boiling point 197°C), octylene glycol (carbon number 8, boiling point 175°C), etc., but are not limited thereto.

[0036] Specific examples of alkylene glycol ethers include ethylene glycol monomethyl ether (carbon number 3, boiling point 124 °C), ethylene glycol monoethyl ether (carbon number 4, boiling point 135 °C), ethylene glycol diethyl ether (carbon number 6, boiling point 121 °C), ethylene glycol monoisopropyl ether (carbon number 5, boiling point 141 °C), ethylene glycol monobutyl ether (carbon number 6, boiling point 171 °C), propylene glycol monomethyl ether (carbon number 4, boiling point 120 °C), propylene glycol monoethyl ether (carbon number 5, boiling point 132 °C), propylene glycol mononormal propyl ether (carbon number 6, boiling point 149 °C), propylene glycol mononormal butyl ether (carbon number 7, boiling point 171 °C), but are not limited thereto. Among these, propylene glycol monomethyl ether is preferred. In the present invention, as the solvent (C), the above solvents can be used alone or in combination of two or more.

[0037] <Adhesive (D)> The adhesive (D) is preferably a urethane resin, an acrylic resin, or a silicate partial hydrolysis condensation oligomer having an alkoxysilyl group or a phenyl group. The alkoxysilyl group can react with the silicate binder (B), colloidal silica (A), or the substrate layer to crosslink. And the urethane resin, the resin having a phenyl group, and the (meth)acrylic resin can enhance the affinity and adhesion to the resin substrate layer. Specific examples of the adhesive (D) include an acrylic resin having an alkoxysilyl group, a urethane resin having an alkoxysilyl group, and a phenyl group-substituted alkyl silicate partial hydrolysis condensation oligomer having an alkoxysilyl group. In order to obtain high adhesion, for example, the weight average molecular weight of the acrylic resin having an alkoxysilyl group by gel permeation (GPC) is preferably 1500 to 100000.

[0038] <Method for producing anchor coating agent> The anchor coating agent of the present invention can be produced, for example, by the following method. 1) A catalyst composed of an acid or a base is dropped into a solvent and stirred and mixed to prepare a catalyst solution. 2) Colloidal silica (A), a silicate binder (B), and a solvent (C) are stirred and mixed. 3) While dropping the catalyst solution prepared above, it is stirred and mixed at 10 to 60 °C for about 1 hour. 4) If necessary, a solvent, an adhesion material (D), and a sliding material (E) are added and stirred and mixed. 5) A solvent is added so that the concentration and viscosity become those according to a desired coating method and coating conditions, and an anchor coating agent is obtained. 6) The obtained anchor coating agent may be filtered, for example, through a filter with a mesh of 0.5 to 2 μm.

[0039] <Method of using the anchor coating agent> The anchor coating agent of the present invention can be applied to a base material layer by cross coating, spray coating, dip coating, spin coating, or roll coating, but is not limited thereto. The anchor coating agent of the present invention cures even at room temperature, but may be baked at a high temperature. Specifically, 1 to 75 minutes is preferable at 15 to 160 °C, 1 to 60 minutes is more preferable, and 45 to 60 minutes at 25 to 50 °C is even more preferable. However, depending on the composition of the anchor coating agent and the composition of the base material layer, it is also possible to dry and cure at a higher temperature and for a longer time than the above. In the case of a room temperature curing type, room temperature drying and curing such as 1 minute, 10 minutes, or 1 hour are possible at 15 to 40 °C. However, it is preferable to contain a solvent that dries sufficiently at room temperature. The standard conditions are 80 °C for 1 to 10 minutes. However, when baked at a high temperature, the hardness of the anchor coating layer increases, but when the base material layer is made of a resin base material, there is a risk of deformation of the base material layer.

[0040] 2. Regarding the high-adhesion laminate The high-adhesion laminate of the present invention is a laminate having at least a base material layer, an anchor coating layer, and a resin layer, and has excellent durability such as interlayer adhesion, hydrolysis resistance, heat resistance, flexibility, etc. It has.

[0041] [Base material layer] The base material layer is an object to be coated with the anchor coating agent of the present invention. The base material layer may be composed of an inorganic material and / or an organic material, and the surface of the base material layer may be a paint layer such as an acrylic clear coating film or a primer layer. Examples of the inorganic material include metal oxides and metals such as ceramics, glass, stainless steel, copper, aluminum, and Ni plating. As an example of the base material using glass, a glass plate, a glass cloth, etc. can also be used. Examples of the organic material include resins such as PMMA, PC, PET, and PP, but are not limited thereto. Among these, PMMA is preferable. The thickness of the base material layer is not particularly limited, but is preferably 0.1 to 5.0 mm. The surface of the base material layer may be subjected to an anti-glare treatment (AG treatment), and it is preferable that the surface roughness Ra is 0.5 to 20 nm by the anti-glare treatment.

[0042] [Anchor coating layer] The anchor coating layer is a layer formed from the anchor coating agent of the present invention, and is excellent in the balance of durability such as high hardness, adhesion, hydrolysis resistance, heat resistance, and flexibility. The thickness of the anchor coating layer is preferably 50 to 2000 nm, more preferably 100 to 1000 nm. It is substantially difficult to form an anchor coating layer thinner than the above range, and even if it is thicker than the above range, the peel strength does not improve so much, and cohesive failure is likely to occur in the anchor coating layer.

[0043] The surface hardness of the anchor coating layer formed from the anchor coating agent of the present invention is preferably H or higher as measured in accordance with JIS K5600-5-4 "Scratch hardness (pencil method)".

[0044] [Resin layer] The resin layer is a layer laminated adjacent to the anchor coating layer formed from the anchor coating agent of the present invention. There is no particular limitation on the resin layer, but it preferably contains a thermoplastic resin. Specific examples of the thermoplastic resin contained include, but are not limited to, PP and PET. There is no particular limitation on the thickness of the resin layer, but it is preferably 1 to 100 μm, and more preferably 2 to 30 μm.

[0045] [Method for manufacturing a high-adhesion laminate] The high-adhesion laminate of the present invention can be produced by a production method including the following steps 1 and 2 using the anchor coating agent of the present invention and a resin composition for the resin layer.

[0046] Step 1; Step of forming an anchor coating layer on a base material layer Base material layer temperature: 15 to 40 °C, Coating method of the anchor coating agent: cross coating, spray coating, dip coating, spin coating, or roll coating, Drying and heat curing conditions of the anchor coating layer: 15 to 160 °C, 1 to 75 minutes, (standard: 80 °C, 1 to 10 minutes), Layer thickness of the anchor coating layer: 100 to 600 nm,

[0047] By adjusting the composition of the anchor coating agent and the process conditions of Step 1, the surface roughness Ra of the anchor coating layer can be adjusted to 0.5 to 20 nm.

[0048] The application of the anchor coating agent may be carried out by any of cross coating, spray coating, dip coating, spin coating, and roll coating. However, spray coating, which is highly productive, easy to adjust the appearance and film thickness, easy to consider the environment, and simple, is preferred.

[0049] As conditions for spray coating, for example, the following are preferred. Nozzle diameter: 0.1 to 10 mm, more preferably 0.1 to 2.0 mm Atomization pressure: 150 to 700 kPa Discharge rate: 0.5 to 20 ml / min Spraying distance: 10 to 200 mm Head speed: 50 to 500 mm / sec Pitch: 0.5 to 10 mm

[0050] When adjusting the surface roughness Ra of the anchor coating layer to 0.5 to 20 nm, the nozzle diameter is particularly preferably 0.1 to 2.0 mm.

[0051] Step 2; Step of forming a resin layer on the anchor coating layer Substrate layer temperature: 15 to 40 °C, Coating method of the resin composition for the resin layer: spray coating, spin coating, or roll coating, Drying and heat curing conditions of the resin layer: 15 to 140 °C, 1 to 60 minutes, Layer thickness of the resin layer: 2 to 30 μm,

[0052] By adjusting the composition of the anchor coating agent and the resin composition for the resin layer, and the process conditions of Step 1 and Step 2, the surface roughness Ra of the anchor coating layer and the resin layer can be adjusted to 0.5 to 20 nm.

[0053] The application of the anchor coating agent and / or the resin composition for the resin layer may be carried out by any of spray coating, spin coating, roll coating, and dip coating. However, spray coating, which is highly productive, easy to adjust the appearance and film thickness, easy to consider the environment, and simple, is preferred.

[0054] As conditions for spray coating, for example, the following are preferable. Nozzle diameter: 0.1 to 10 mm, more preferably 0.1 to 2.0 mm Atomization pressure: 150 to 700 kPa Discharge rate: 0.5 to 20 ml / min Spraying distance: 10 to 200 mm Head speed: 50 to 500 mm / sec Pitch: 0.5 to 10 mm

[0055] When adjusting the surface roughness Ra of the anchor coating layer and the resin layer to 0.5 to 20 nm, the nozzle diameter is particularly preferably 0.1 to 2.0 mm.

[0056] 3. Regarding the metal plating laminate The metal plating laminate of the present invention is a laminate having at least a base material layer, an anchor coating layer, and a metal plating layer, and has excellent durability such as interlayer adhesion, hydrolysis resistance, heat resistance, and flexibility.

[0057] [Base material layer] The base material layer is an object to be coated with the anchor coating agent of the present invention. The base material layer may be composed of an inorganic material and / or an organic material, and the surface of the base material layer may be a paint layer such as an acrylic clear coating film. Examples of inorganic materials include metal oxides and metals such as ceramics, glass, stainless steel, copper, aluminum, and Ni plating. As an example of a base material using glass, a glass plate, a glass cloth, etc. can also be used. Examples of organic materials include resins such as PMMA, PC, PET, and PP, but are not limited thereto. Among these, PMMA is preferable. The thickness of the base material layer is not particularly limited, but is preferably 0.1 to 5.0 mm. The surface of the base material layer may be subjected to an antiglare treatment (AG treatment), and preferably has a surface roughness Ra of 0.5 to 20 nm by the antiglare treatment.

[0058] [Anchor coating layer] The anchor coating layer is a layer formed from the anchor coating agent of the present invention, and is excellent in the balance of durability such as high hardness, adhesion, hydrolysis resistance, heat resistance, and flexibility. The surface roughness Ra of the anchor coating layer is preferably 0.5 to 20 nm, more preferably 2 to 10 nm. If the surface roughness Ra is within the above range, it is easy to obtain high adhesion with the upper and lower layers. The thickness of the anchor coating layer is preferably 50 to 2000 nm, more preferably 100 to 1000 nm. It is substantially difficult to form an anchor coating layer thinner than the above range, and even if it is thicker than the above range, the peel strength does not improve so much, and cohesive failure is likely to occur in the anchor coating layer.

[0059] The surface hardness of the anchor coating layer is preferably H or more as measured in accordance with JIS K5600-5-4 "Scratch hardness (pencil method)".

[0060] [Metal plating layer] The metal plating layer is a layer laminated adjacent to the anchor coating layer formed from the anchor coating agent of the present invention. Examples of the metal species contained in the metal plating layer include, but are not limited to, nickel, copper, etc. The thickness of the metal plating layer is preferably 0.1 to 50 μm, more preferably 1 to 10 μm. It is substantially difficult to form a metal plating layer thinner than the above range, and it is not realistic to form a metal plating layer thicker than the above range.

[0061] [Method for manufacturing metal plating laminate] The metal plating laminate of the present invention can be produced by a manufacturing method including the following steps 1 and 2 using the anchor coating agent of the present invention and the metal species for plating.

[0062] Step 1; Anchor coating layer formation step on the base material layer Base material layer temperature: 15 to 40 °C, Coating method of the anchor coating agent: cross coating, spray coating, dip coating, spin coating, or roll coating, Drying and heat curing conditions of the anchor coating layer: 15 to 160 °C, 1 to 75 minutes, (standard: 80 °C, 1 to 10 minutes), Layer thickness of the anchor coating layer: 100 to 600 nm,

[0063] By adjusting the composition of the anchor coating agent and the process conditions of Step 1, the surface roughness Ra of the anchor coating layer can be adjusted to 0.5 to 20 nm.

[0064] The anchor coating agent can be applied by any of cross coating, spray coating, dip coating, spin coating, or roll coating. However, spray coating is preferred because it has high productivity, is easy to adjust the appearance and film thickness, is environmentally friendly, and is simple.

[0065] As the conditions for spray coating, for example, the following are preferred. Nozzle diameter: 0.1 to 10 mm, more preferably 0.1 to 2.0 mm Atomization pressure: 150 to 700 kPa Discharge rate: 0.5 to 20 ml / min Spraying distance: 10 to 200 mm Head speed: 50 to 500 mm / sec Pitch: 0.5 to 10 mm

[0066] When adjusting the surface roughness Ra of the anchor coating layer to 0.5 to 20 nm, the nozzle diameter is particularly preferably 0.1 to 2.0 mm.

[0067] Step 2; Process of forming a metal plating layer on the anchor coating layer There is no particular limitation on the method for forming the metal plating layer. For example, general metal plating layer forming methods such as electroless plating can be applied.

Example

[0068] Hereinafter, the present invention will be specifically described by way of examples. The present invention is not limited to the following examples. The raw materials used in the examples are as follows.

[0069] <Raw materials> [Colloidal silica] · Colloidal silica sol 1: Snowtex ST-OUP manufactured by Nissan Chemical Industries, Ltd. Acidic sol type chain nano silica sol. Particle size 12 nm, solid content 15 wt%, solvent is water. · Colloidal silica sol 2: Snowtex ST-PS-SO manufactured by Nissan Chemical Industries, Ltd. Acidic sol type pearl necklace shaped nano silica sol. Particle size 15 nm, solid content 15 wt%, solvent is water. · Colloidal silica sol 3: Snowtex IPA-ST manufactured by Nissan Chemical Industries, Ltd. Nano silica sol. Particle size 12 nm, solid content 30 wt%, solvent is IPA.

[0070] [Silicate oligomer] · Silicate oligomer 1: Silicate 40 manufactured by Tama Chemical Industry Co., Ltd. A mixture of polyethyl silicate, tetraethoxysilane and solvent, non-volatile content 100 mass%. 60 - 70 mass% of the non-volatile content is polyethyl silicate. · Aminosilane 1: KBM-903 manufactured by Shin-Etsu Chemical Co., Ltd. 3-Aminopropyltrimethoxysilane. Non-volatile content 100 mass%. · Epoxy group-containing silicate oligomer 1: KR-517 manufactured by Shin-Etsu Chemical Co., Ltd. Epoxy group-containing silicate oligomer. Non-volatile content 100 mass%.

[0071] [Adhesive] · Adhesive 1: 8SQ-1100 manufactured by Daisheng Fine Chemical Co., Ltd. Silicon-modified acrylic polymer, non-volatile content 50 mass%.

[0072] [Commercially available anchor coating agent] · Commercially available AC agent 1: Aron Alpha Extra impact resistant type manufactured by Toagosei Co., Ltd. · Commercially available AC agent 2: Universal Bond manufactured by Daikoukaken Co., Ltd. <Synthesis example> [Preparation of Nitric Acid Solution 1] The following were mixed to obtain Nitric Acid Solution 1 as a catalyst. 10% Aqueous Nitric Acid 1.0 part by mass Water 3.0 parts by mass Ethanol 30 parts by mass

[0073] [Preparation of Silicate Binder 1] First, the following were mixed to obtain a mixed solution. Silicate Oligomer 1 8.0 parts by mass Ethanol 30 parts by mass While dropping 34 parts by mass of Nitric Acid Solution 1 obtained above, the mixture was stirred and mixed at 40°C for 1 hour. Next, the following were further added and stirred and mixed to obtain Silicate Binder 1. Ethanol 28.0 parts by mass The weight-average molecular weight of Silicate Binder (B) contained in the obtained Silicate Binder 1 was 3700.

[0074] [Example] [Example 1] The following were stirred and mixed at 40°C for 1.5 hours to obtain an anchor coating agent. Colloidal Silica Sol 1 14.2 parts by mass Silicate Binder 1 4.7 parts by mass Ethanol 81.1 parts by mass Using the obtained anchor coating agent, an anchor coating layer was formed on various base material layers, and various evaluations were performed. The anchor coating layer was formed by spin-coating the anchor coating agent on a base material layer at 25°C to a film thickness of about 200 nm using a spin coater (MS-A100, manufactured by Mikasa Co., Ltd.), followed by drying and curing treatment.

[0075] [Examples 2 to 9, Comparative Examples 1 to 3] According to the formulations in Table 1, stirring and mixing were carried out in the same manner as in Example 1 to obtain an anchor coating agent. Then, an anchor coating layer was formed on the base material layer in the same manner as in Example 1 and evaluated in the same manner as in Example 1.

[0076] [Comparative Examples 4 and 5] According to Table 1, using commercially available AC agent 1 or commercially available AC agent 2, an anchor coating layer was formed on the base material layer in the same manner as in Example 1 and evaluated in the same manner as in Example 1.

[0077] [Evaluation Method] [Molecular Weight Measurement] Using a GPC device (HLC-8320GPC manufactured by Tosoh Corporation, THF solvent), the polystyrene-equivalent weight-average molecular weight was measured.

[0078] [Surface Hardness of Anchor Coating Layer] The surface hardness of the anchor coating layer was measured in accordance with JIS K5600 "4.4 Scratch Hardness (Pencil Method) of General Test Methods for Paints".

[0079] [Appearance of Anchor Coating Layer] First, the anchor coating agent was applied onto a degreased glass substrate and dried and cured at 80 °C for 30 minutes to form an anchor coating layer. Then, a black tape was attached to the back surface of the glass substrate layer, sunlight was applied, and the presence or absence and degree of abnormalities of the anchor coating layer formed on the glass substrate layer were observed visually. The meanings of the symbols in the table are as follows. 〇: Uniform and transparent appearance △: Some unevenness or other abnormalities ×: Strong unevenness or other abnormalities

[0080] [Adhesion of Anchor Coating Layer] First, the anchor coating agent was applied onto a degreased glass substrate and a PC resin substrate and dried and cured at 80 °C for 30 minutes to form an anchor coating layer. Then, after attaching cellophane tape to the anchor coating layer and peeling it off, the peeling condition between the anchor coating layer and the base material layer and the appearance of the anchor coating layer were evaluated by visual appearance. The meanings of the symbols in the table are as follows. ◎: The tape is cut and all remains, and the anchor coating layer has no change in appearance. 〇: A part of the tape remains, and the anchor coating layer has no change in appearance. 〇△: The tape peels off, and the anchor coating layer has no change in appearance. △: Agglomeration destruction occurs in the anchor coating layer. ×: Complete peeling occurs at the interface between the anchor coating layer and the substrate layer.

[0081] [Plating property] First, an anchor coating agent was applied to a degreased glass substrate and dried and cured at 80 °C for 10 minutes to form an anchor coating layer. Then, the surface charge of the formed anchor coating layer was adjusted, and after loading the catalyst, a Ni plating layer was formed on the anchor coating layer by electroless plating using an electroless Ni plating apparatus (ICP Nicoron manufactured by Okuno Pharmaceutical Co., Ltd.). Cuts were made in the formed Ni plating layer with a cutter knife so that 10×10 grids could be formed in an area of 10 mm×10 mm, the tape was pasted and peeled off, and the number of peeled grids was counted. The meanings of the symbols in the table are as follows. 〇: No peeling 〇△: The number of peeled ones is 1 - 5 △: The number of peeled ones is 5 - 80 ×: The number of peeled ones is 80 or more

[0082]

Table 1

[0083]

Table 2

[0084]

Table 3

[0085] <Summary of Results> The anchor coating agents of all the examples showed an excellent balance of appearance, high surface hardness, high adhesion to the substrate layer, and excellent plating properties, while the treatment agents of the comparative examples showed inferior results in some respects.

Industrial Applicability

[0086] The low-reflection treatment agent of the present invention can be used for electrical components and electronic components using glass, resin, and metal lead frames for electronic devices and automobiles, etc., and can improve the bonding and adhesion between various metals, resins, and metal plating surfaces.

Explanation of Symbols

[0087] 1 High-adhesion laminate 2 Substrate layer 3 Anchor coating layer 4 Resin layer 5 Metal plating layer

Claims

1. An anchor coating agent for enhancing the adhesiveness between a base material layer and a resin layer or a metal plating layer by forming an anchor coating layer between the base material layer and the resin layer or the metal plating layer, The anchor coating agent contains colloidal silica (A), a silicate binder (B), and a solvent (C). The colloidal silica (A) may contain chain silica and / or pearl necklace-shaped silica. The above-mentioned anchor coating agent.

2. The anchor coating agent according to Claim 1, wherein the content of colloidal silica (A) in the solid content of the anchor coating agent is 30% by mass or more and 90% by mass or less.

3. The anchor coating agent according to Claim 1, wherein 60% by mass or more of the colloidal silica (A) is chain silica and / or pearl necklace-shaped silica.

4. The anchor coating agent according to Claim 1, further containing an adhesion promoter (D).

5. A high-adhesion laminate having an anchor coating layer and a resin layer adjacent to each other in this order on a base material layer, The anchor coating layer is a layer made of the anchor coating agent according to any one of Claims 1 to 4. The above-mentioned high-adhesion laminate.

6. A metal plating laminate having an anchor coating layer and a metal plating layer adjacent to each other in this order on a base material layer, The anchor coating layer is a layer made of the anchor coating agent according to any one of Claims 1 to 4. The above-mentioned metal plating laminate.

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