JP6320669B1 - Article - Google Patents

Abstract

It is a laminate in which an adhesive layer is provided on at least one side of a resin film, the resin constituting the resin film is a semi-aromatic polyamide and / or a polyimide resin, and the adhesive layer has an amine value of 1.0 mgKOH / A laminate comprising a dimer acid-based polyamide resin less than g and a crosslinking agent.

Description

  The present invention relates to a laminate comprising a resin film and an adhesive layer and suitable for applications exposed to high temperatures during production and use, and having excellent heat resistance.

  In recent years, with the miniaturization, weight reduction, and high density of electronic devices, flexible printed wiring boards built in electronic devices are increasingly multilayered using adhesive sheets. In an environment where the adhesive sheet passes through a process that is processed at a high temperature of 200 ° C. or higher such as a reflow soldering process in the production of a flexible printed wiring board, is exposed to a high temperature and high humidity for a long time, or is repeatedly subjected to a thermal history. Therefore, it is not sufficient that the material itself constituting the adhesive sheet has heat resistance, and the adhesiveness is required to be maintained even in the high temperature environment.

  Patent Document 1 discloses a heat resistant adhesive sheet in which a polyimide resin film, which is a heat resistant resin film, is used as a base film, and a thermosetting adhesive is laminated thereon.

JP 2010-285463 A

  However, in the heat-resistant adhesive sheet disclosed in Patent Document 1, since the resin constituting the adhesive layer is thermosetting, in order to make the resin semi-cured on the base film, substantially 10 minutes. Heating was necessary, and it took time to use as an adhesive sheet. Moreover, also in adhesion | attachment with a to-be-adhered body, it took a long time of 1 hour to heat-press.

  The present invention is a laminate formed by forming an adhesive layer on a heat-resistant resin film, and the adhesive layer of this laminate can be bonded to an adherend by a short-time thermocompression bonding. It is a technical problem to provide a laminate that is excellent in adhesiveness and does not deteriorate the adhesiveness even at high temperatures.

As a result of intensive studies to solve the above problems, the present inventors have been able to laminate an adhesive layer containing a dimer acid-based polyamide resin on a resin film composed of a specific resin in a short time. The body is excellent in the adhesion between the resin film and the adhesive layer, can be bonded to the adherend in a short time, and the adhesion with the adherend is found to be excellent at both normal temperature and high temperature, The present invention has been reached.
That is, the gist of the present invention is as follows.
(1) An article in which a laminate in which an adhesive layer is provided on at least one surface of a resin film and a hard coat layer are bonded ,
The resin constituting the resin film is a semi-aromatic polyamide and / or a polyimide resin,
Adhesive layer, amine value is characterized by containing a dimer acid-based polyamide resin is less than 1.0 mgKOH / g, a crosslinking agent article.
(2) The article according to (1), comprising 0.5 to 50 parts by mass of a crosslinking agent with respect to 100 parts by mass of the dimer acid-based polyamide resin.
(3) The article according to (1) or (2), wherein the crosslinking agent is an oxazoline compound.
(4) The article according to any one of (1) to (3), wherein the dimer acid-based polyamide resin has an acid value of 1 to 20 mgKOH / g .
(5 ) The article according to any one of (1) to (4), wherein the haze is 5.0% or less.
( 6 ) The article according to any one of ( 1 ) to ( 5 ), wherein the article is a flexible display article .

The laminate of the present invention is composed of an adhesive layer containing a dimer acid-based polyamide resin and a crosslinking agent, and a resin film made of a specific resin, and the adhesive layer is formed on the resin film in a short time. This adhesive layer is excellent in adhesion to the resin film.
In addition, the adhesive layer of the laminate of the present invention can be bonded to the adherend by short-time thermocompression bonding, and is excellent in adhesion to the adherend at both normal temperature and high temperature. Specific examples of the adherend include a resin film such as polyimide, a metal plate, and a hard coat layer formed by applying a coating liquid on the surface of the adhesive layer.
The laminate of the present invention can be used in any mode of a single-sided adhesive sheet in which an adhesive layer is provided on one side of a resin film or a double-sided adhesive sheet in which an adhesive layer is provided on both sides of a resin film.

Hereinafter, the present invention will be described in detail.
The laminate of the present invention is one in which an adhesive layer is provided on at least one side of a resin film, and the adhesive layer contains a dimer acid-based polyamide resin and a crosslinking agent.

<Dimer acid polyamide resin>
Since the dimer acid-based polyamide resin constituting the adhesive layer has a large hydrocarbon group, it is excellent in flexibility as compared with resins such as nylon 6, nylon 66, and nylon 12, which are widely used as polyamide resins.
In the present invention, the dimer acid-based polyamide resin contains dimer acid as the dicarboxylic acid component, and the dimer acid is preferably contained in an amount of 50 mol% or more, more preferably 60 mol% or more of the entire dicarboxylic acid component. More preferably, it is more preferable to contain 70 mol% or more. When the ratio of the dimer acid is less than 50 mol%, it becomes difficult to achieve the characteristics and effects of the dimer acid-based polyamide resin. As a result, sufficient adhesion with the resin film as the base material and the adherend In some cases, sufficient adhesion cannot be obtained.

  Here, the dimer acid is obtained by dimerizing an unsaturated fatty acid having 18 carbon atoms such as oleic acid or linoleic acid, and is a monomer if it is 25% by mass or less of the dimer acid component. Monomer acid (18 carbon atoms), trimer acid (carbon number 54) which is a trimer, other polymerized fatty acids having 20 to 54 carbon atoms, and further hydrogenated to lower the degree of unsaturation Good. Dimer acids are commercially available as the Hari dimer series (manufactured by Harima Kasei Co., Ltd.), the pre-pole series (manufactured by Croda Japan Co., Ltd.), the Tsuno Dime series (manufactured by Tsukino Food Industry Co., Ltd.), etc.

When a component other than dimer acid is used as the dicarboxylic acid component of the dimer acid-based polyamide resin, it is preferable to use adipic acid, azelaic acid, sebacic acid, pimelic acid, suberic acid, nonanedicarboxylic acid, fumaric acid, etc. By containing, control of the softening point of resin, adhesiveness, etc. becomes easy.
As the diamine component of the dimer acid polyamide resin, ethylene diamine, hexamethylene diamine, tetramethylene diamine, pentamethylene diamine, m-xylene diamine, phenylene diamine, diethylene triamine, piperazine, etc. can be used, among which ethylene diamine, hexamethylene. Diamine, diethylenetriamine, m-xylenediamine and piperazine are preferred.
When polymerizing the dimer acid-based polyamide resin, the polymerization degree or acid value or amine value of the resin can be controlled by changing the charging ratio of the dicarboxylic acid component and the diamine component.

In the present invention, the amine value of the dimer acid polyamide resin needs to be less than 1.0 mgKOH / g, preferably less than 0.7 mgKOH / g, and less than 0.4 mgKOH / g. More preferred. When a dimer acid-based polyamide resin having an amine value of 1.0 mgKOH / g or more is used for the adhesive layer, the heat resistance of the adhesive layer may decrease, and even when used as a primer or as a primer. Adhesiveness with a to-be-adhered body may fall.
The acid value of the dimer acid-based polyamide resin is preferably 1 to 20 mgKOH / g, more preferably 1 to 15 mgKOH / g, from the viewpoint of adhesion to an adherend when used as a primer. Preferably, it is 3-12 mgKOH / g, more preferably 5-12 mgKOH / g. Further, from the viewpoint of adhesion to an adherend such as a metal plate, it is preferably 1 to 20 mgKOH / g, more preferably 1 to 15 mgKOH / g, and most preferably 5 to 12 mgKOH / g. preferable. When the acid value of the dimer acid-based polyamide resin is less than 1 mgKOH / g, the adhesion with the resin film as the base material and the adhesion with the resin film or metal as the adherend may be insufficient. When it exceeds 20 mgKOH / g, the adhesiveness with the resin film which is a base material may become inadequate.
The acid value is defined as the number of milligrams of potassium hydroxide required to neutralize the acidic component contained in 1 g of resin. On the other hand, the amine value is represented by the number of milligrams of potassium hydroxide that is molar equivalent to the base component in 1 g of the resin. Both are measured by the method described in JIS K2501.

  The softening point of the dimer acid-based polyamide resin is preferably 70 to 250 ° C, more preferably 80 to 240 ° C, and further preferably 80 to 200 ° C. When the softening point is less than 70 ° C., the resulting adhesive layer tends to have low heat resistance, and tends to increase tackiness at room temperature. On the other hand, when the softening point exceeds 250 ° C., the resulting adhesive layer has insufficient resin fluidity when bonded, and sufficient adhesiveness may not be obtained.

<Crosslinking agent>
The adhesive layer in the present invention contains a dimer acid polyamide resin and a crosslinking agent. By crosslinking the dimer acid-based polyamide resin, it is possible to obtain an adhesive layer that exhibits heat resistance even when heated to a temperature higher than the softening point of the resin, and it is possible to obtain a laminate having excellent hot adhesiveness.

  Any crosslinking agent can be used as long as it can crosslink dimer acid polyamide resins. For example, hydrazide compounds, isocyanate compounds, melamine compounds, urea compounds, epoxy compounds, carbodiimide compounds, oxazoline compounds, and those having self-crosslinkability and those having a multivalent coordination position can be mentioned. Or it can mix and use. Among these, from the viewpoint of adhesion to a resin film as a substrate and adhesion to a resin film or metal as an adherend, an oxazoline compound, a carbodiimide compound, an epoxy compound, and an isocyanate compound are preferable, and an oxazoline compound is more preferable.

  In the present invention, a commercially available crosslinking agent may be used because it is easily available. Specifically, APA series (APA-M950, APAM980, APA-P250, APA-P280, etc.) manufactured by Otsuka Chemical Co., Ltd. can be used as the hydrazide compound. As the isocyanate compound, BASONAT PLR8878 manufactured by BASF, Bassonate HW-100, Bayhydur 3100 manufactured by Sumitomo Bayer Urethane Co., Ltd., and Bihydur VPLS2150 / 1 can be used. As a melamine compound, Cymel 325 manufactured by Mitsui Cytec Co., Ltd. can be used. As the urea compound, becamine series manufactured by DIC, etc. can be used. As the epoxy compound, Denasel series (EM-150, EM-101, etc.) manufactured by Nagase Chemtech, Adeka Resin EM-0517, EM-0526, EM-051R, EM-11-50B manufactured by ADEKA, etc. can be used. . As the carbodiimide compound, carbodilite series (SV-02, V-02, V-02-L2, V-04, E-01, E-02, V-01, V-03, V-, manufactured by Nisshinbo Chemical Co., Ltd.) 07, V-09, V-05) and the like can be used. As the oxazoline compound, EPOCROSS series (WS-500, WS-700, K-1010E, K-1020E, K-1030E, K-2010E, K-2020E, K-2030E) manufactured by Nippon Shokubai Co., Ltd. can be used. These are commercially available as dispersions or solutions containing a cross-linking agent.

<Adhesive layer>
The adhesive layer in the present invention contains a dimer acid polyamide resin and a crosslinking agent, and preferably contains 0.5 to 50 parts by mass of the crosslinking agent with respect to 100 parts by mass of the dimer acid polyamide resin. When the content of the crosslinking agent is less than 0.5 parts by mass, it becomes difficult to obtain sufficient heat resistance in the adhesive layer. On the other hand, when the content exceeds 50 parts by mass, the liquid stability and processing of the adhesive layer-forming coating agent described later The adhesiveness with the resin film which is a base material, the adhesiveness with the resin film and metal which is a to-be-adhered body, and the basic performance as an adhesive layer may be difficult to obtain.

  The thickness of the adhesive layer in the laminate is not particularly limited and is preferably 0.01 to 50 μm, but can be arbitrarily selected depending on the method of laminating the adherend. When pasting together by hot pressing, it is preferably 0.1 to 50 μm, more preferably 0.5 to 20 μm, and most preferably 1.0 to 15 μm. When coating a functional layer as a primer layer, it is preferably 0.01 to 30 μm, more preferably 0.03 to 20 μm, and most preferably 0.05 to 10 μm. If the thickness is less than 0.01 μm, the adhesiveness may not be sufficiently exhibited. On the other hand, if the thickness exceeds 50 μm, the adhesiveness may be saturated, which may be disadvantageous in terms of cost.

<Resin film>
In the laminate of the present invention, an adhesive layer containing a dimer acid-based polyamide resin and a cross-linking agent is provided on at least one surface of a resin film, and has excellent adhesiveness with the adhesive layer. In order to use as a heat resistant adhesive sheet, the resin constituting the resin film needs to be a semi-aromatic polyamide and / or a polyimide resin.

The semi-aromatic polyamide is composed of a dicarboxylic acid component and a diamine component, and has an aromatic component in the dicarboxylic acid component or diamine component.
The dicarboxylic acid component constituting the semi-aromatic polyamide is preferably terephthalic acid as a main component, and as dicarboxylic acid components other than terephthalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid , Aliphatic dicarboxylic acids such as dodecanedioic acid, tetradecanedioic acid and octadecanedioic acid, and aromatics such as 1,4-naphthalenedicarboxylic acid, 1,3-naphthalenedicarboxylic acid, 1,2-naphthalenedicarboxylic acid and isophthalic acid Dicarboxylic acid is mentioned. The proportion of terephthalic acid in the dicarboxylic acid component is preferably 60 to 100 mol%.

  The diamine component constituting the semi-aromatic polyamide is preferably composed mainly of an aliphatic diamine having 4 to 15 carbon atoms, such as 1,4-butanediamine, 1,5-pentanediamine, and 1,6-hexane. Diamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 2-methyl-1,8-octanediamine, 4-methyl-1,8-octanediamine, 1,10-decanediamine 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine, 1,15-pentadecanediamine, and the like. These may be used alone or in combination of two or more.

  Among the semi-aromatic polyamides obtained by the combination of the monomers, from the viewpoint of heat resistance and film molding processability, a dicarboxylic acid component consisting of only terephthalic acid (100 mol% terephthalic acid), and 1,9- Semi-aromatic polyamides comprising a diamine component containing 60 to 100 mol% of nonanediamine and 2-methyl-1,8-octanediamine in total in the diamine component and a diamine component containing 1,10-decanediamine are preferred.

  The semi-aromatic polyamide may be copolymerized with lactams such as ε-caprolactam, ζ-enantolactam, η-capryllactam, and ω-laurolactam as long as the object of the present invention is not impaired.

  The type and copolymerization ratio of the monomers constituting the semiaromatic polyamide are preferably selected so that the Tm (melting point) of the obtained semiaromatic polyamide is in the range of 280 to 350 ° C. By setting the Tm of the semi-aromatic polyamide in the above range, the thermal decomposition of the semi-aromatic polyamide when processed into a resin film can be efficiently suppressed. If the Tm is less than 280 ° C., the resulting resin film may have insufficient heat resistance. On the other hand, if Tm exceeds 350 ° C., thermal decomposition may occur during the production of the resin film.

  A commercially available product can be suitably used as the semi-aromatic polyamide. Examples of such commercially available products include “Genesta (registered trademark)” manufactured by Kuraray Co., Ltd., “Zecott (registered trademark)” manufactured by Unitika, “Reny (registered trademark)” manufactured by Mitsubishi Engineering Plastics, and Mitsui Chemicals Examples include “Aalen (registered trademark)”, “Ultramid (registered trademark)” manufactured by BASF Corporation.

  The semi-aromatic polyamide can be produced using any known method. Examples thereof include a solution polymerization method or an interfacial polymerization method using an acid chloride and a diamine component as raw materials. Alternatively, a method of preparing a prepolymer using a dicarboxylic acid component and a diamine component as raw materials and increasing the molecular weight of the prepolymer by melt polymerization or solid phase polymerization can be mentioned.

  Furthermore, you may use terminal blocker with a diamine component, a dicarboxylic acid component, and a polymerization catalyst as needed. The end-capping agent is not particularly limited as long as it is a monofunctional compound having reactivity with an amino group or a carboxyl group at the end of the semi-aromatic polyamide, from the viewpoint of suppressing thermal decomposition or suppressing increase in molecular weight. Examples include monocarboxylic acids, monoamines, acid anhydrides, monoisocyanates, monohalides, monoesters, and monoalcohols.

  The polyimide resin constituting the resin film is a polymer containing an imide bond in the repeating unit, and examples thereof include polyimide, polyetherimide, and polyamideimide.

  The polyimide resin is produced by any known method. For example, in a polymer in which a tetracarboxylic acid component and a diamine component are imide-bonded, a polyimide resin obtained by reacting a tetracarboxylic dianhydride and a diamine compound is used. It is preferable to be obtained by imidizing a resin precursor (polyamic acid).

Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, and 2,2-bis (2,3-dicarboxyphenyl). -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane Dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 2,2-bis [4- (2,3- Dicarboxyphenoxy) phenyl] propane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride. These tetracarboxylic dianhydrides may be used alone or in combination of two or more.
Examples of the diamine compound include m-phenylenediamine, p-phenylenediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, and 3,3'-diaminodiphenyl sulfone. 2,2-bis (4-aminophenoxyphenyl) propane, 2,2-bis (4-aminophenoxyphenyl) hexafluoropropane, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis ( 4-aminophenoxy) benzene, 2,4-diaminotoluene, 2,6-diaminotoluene, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diamino-2,2-dimethylbiphenyl 2,2-bis (trifluoromethyl) -4,4'-di Mino biphenyl, and the like. These diamine compounds may be used alone or in combination of two or more.
Due to its excellent heat resistance, mechanical strength, electrical properties, and chemical resistance, the polyimide resin is composed of tetracarboxylic dianhydride pyromellitic dianhydride and diamine compound 4,4'-diaminodiphenyl ether. A configuration in which the tetracarboxylic dianhydride is 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and the diamine compound is p-phenylenediamine is preferable.

The polyimide resin may be a polyamideimide, which is a polymer in which a tricarboxylic acid component and a diamine component are bonded to an imide bond and an amide bond.
Examples of the tricarboxylic acid component include trimellitic acid, diphenyl ether-3,3 ′, 4′-tricarboxylic acid, diphenylsulfone-3,3 ′, 4′-tricarboxylic acid, benzophenone-3,3 ′, 4′-tricarboxylic acid, and the like. Examples of the diamine component include those exemplified as the diamine compound constituting the polyimide resin.
Polyamideimide can usually be produced by polymerizing by reaction of trimellitic anhydride and diisocyanate, or by reaction of trimellitic anhydride chloride and diamine, and then imidizing.

  The method for producing a resin film from the above semi-aromatic polyamide or polyimide resin is not particularly limited, and examples thereof include an extrusion method or a solvent casting method, and the resin film constituting the laminate of the present invention is Any of these methods may be used.

The resin film is required to be composed of the above resin, but includes known additives and stabilizers, such as antistatic agents, plasticizers, lubricants, antioxidants, etc., as long as the effects of the present invention are not impaired. It may be.
The resin film may be subjected to a corona treatment, a plasma treatment, an ozone treatment, a chemical treatment, a solvent treatment, or the like as a pretreatment on the surface in consideration of adhesiveness when laminated with the adhesive layer.
The thickness of the resin film is preferably 0.5 μm to 1.5 mm, more preferably 15 to 200 μm, and still more preferably 25 to 100 μm. If the thickness of the resin film is less than 0.5 μm, the production is difficult, and if it exceeds 1.5 mm, it is difficult to handle, which is not preferable. The resin film may be an unstretched film or a stretched film.

  The resin film constituting the laminate is required to be excellent in transparency depending on the use of the laminate. Usually, the transparency of a film is represented by haze and total light transmittance. The resin film constituting the laminate of the present invention preferably has a haze of less than 15%, more preferably less than 10%, and a total light transmittance of preferably 60% or more, 80% More preferably.

<Manufacture of laminates>
The laminate of the present invention is one in which an adhesive layer is provided on at least one side of a resin film, for example, an adhesive layer forming coating containing a dimer acid-based polyamide resin and a crosslinking agent is applied to the resin film, It can be manufactured by drying.

(Coating agent for adhesive layer formation)
The adhesive layer-forming coating agent is a dispersion obtained by dispersing or dissolving a dimer acid-based polyamide resin and a crosslinking agent in an aqueous medium or solvent, and is an aqueous dispersion dispersed in an aqueous medium in consideration of the working environment. Preferably there is. The aqueous medium is a liquid mainly composed of water, and may contain a basic compound or a hydrophilic organic solvent described later.

In order to disperse the dimer acid-based polyamide resin in an aqueous medium with good stability, it is preferable to use a basic compound. By using the basic compound, some or all of the carboxyl groups contained in the dimer acid-based polyamide resin are neutralized, carboxyl anions are generated, and the electric repulsive force releases the aggregation between the resin fine particles, The dimer acid-based polyamide resin is stably dispersed in the aqueous medium.
The aqueous dispersion in the present invention has a carboxyl group in the dimer acid-based polyamide resin neutralized with a basic compound, and can maintain a stable form in an alkaline region. The pH of the aqueous dispersion is preferably in the range of 7-13. As the basic compound, a basic compound having a boiling point of less than 185 ° C. at normal pressure is preferable.

Examples of the basic compound having a boiling point of less than 185 ° C. at normal pressure include amines such as ammonia and organic amine compounds. Specific examples of the organic amine compound include triethylamine, N, N-dimethylethanolamine, isopropylamine, iminobispropylamine, ethylamine, diethylamine, 3-ethoxypropylamine, 3-diethylaminopropylamine, sec-butylamine, propylamine, Examples include methylaminopropylamine, methyliminobispropylamine, 3-methoxypropylamine, monoethanolamine, morpholine, N-methylmorpholine, N-ethylmorpholine and the like. As a basic compound having a boiling point of less than 185 ° C. at normal pressure, triethylamine and N, N-dimethylethanolamine are particularly preferable.
When the boiling point of the basic compound at normal pressure exceeds 185 ° C., it becomes difficult to volatilize the basic compound, particularly the organic amine compound by drying, when applying a water-based coating to form a coating film. May adversely affect hygiene and coating properties.

  The content of the basic compound in the aqueous dispersion is preferably 0.01 to 100 parts by mass, more preferably 1 to 40 parts by mass, and further preferably 1 to 15 parts by mass with respect to 100 parts by mass of the resin solid content. preferable. When the content of the basic compound is less than 0.01 parts by mass, the effect of adding the basic compound is poor, and it becomes difficult to obtain an aqueous dispersion excellent in dispersion stability. On the other hand, when the content of the basic compound exceeds 100 parts by mass, the aqueous dispersion tends to be colored or gelled, and the pH of the emulsion tends to be too high.

  In the present invention, when an aqueous dispersion is used as the adhesive layer-forming coating agent, it is preferable that the boiling point at normal pressure is 185 ° C. or higher or that a non-volatile aqueous auxiliary agent is not contained. A boiling point at normal pressure of 185 ° C. or higher, or a non-volatile aqueous auxiliary agent refers to an emulsifier component or a compound having a protective colloid effect. That is, in the present invention, a stable aqueous dispersion having a fine resin particle size can be obtained without using an aqueous additive. Since the use of an aqueous additive does not immediately reduce the stability of the aqueous dispersion, the present invention does not preclude the use of an aqueous additive. In the present invention, the aqueous dispersion is clearly distinguished from that obtained by a method based on the so-called phase inversion emulsification method containing an aqueous auxiliary agent as an essential component. Therefore, an aqueous auxiliary agent is not used as much as possible. It is particularly preferred that it is not used at all. However, after obtaining the aqueous dispersion, an aqueous auxiliary agent may be used positively depending on the purpose, for example, when newly obtaining another coating material containing the aqueous dispersion. Needless to say, an aqueous auxiliary agent may be added accordingly.

Examples of the emulsifier component include a cationic emulsifier, an anionic emulsifier, a nonionic emulsifier, and an amphoteric emulsifier. In addition to those generally used for emulsion polymerization, surfactants are also included. For example, anionic emulsifiers include higher alcohol sulfates, higher alkyl sulfonates, higher carboxylates, alkyl benzene sulfonates, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkyl phenyl ether sulfate salts, vinyl sulfosuccinates. Nonionic emulsifiers include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol fatty acid ester, ethylene oxide propylene oxide block copolymer, polyoxyethylene fatty acid amide, ethylene oxide-propylene oxide Examples thereof include a compound having a polyoxyethylene structure such as a copolymer and a sorbitan derivative. Examples of amphoteric emulsifiers include lauryl betaine and lauryl dimethylamine oxide.
The compounds having protective colloidal action include polyvinyl alcohol, carboxyl group-modified polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, modified starch, polyvinyl pyrrolidone, polyacrylic acid and salts thereof, carboxyl group-containing polyethylene wax, carboxyl group-containing Acid-modified polyolefin waxes having a number average molecular weight of usually 5000 or less, such as polypropylene wax and carboxyl group-containing polyethylene-propylene wax, and salts thereof, acrylic acid-maleic anhydride copolymers and salts thereof, styrene- (meth) acrylic acid Copolymer, ethylene- (meth) acrylic acid copolymer, isobutylene-maleic anhydride alternating copolymer, (meth) acrylic acid- (meth) acrylic Carboxyl group-containing polymer having an unsaturated carboxylic acid content of 10% by mass or more, such as a sulfonate ester copolymer, and salts thereof, polyitaconic acid and salts thereof, water-soluble acrylic copolymers having amino groups, gelatin, and gum arabic And compounds generally used as fine particle dispersion stabilizers, such as casein.

Next, a method for aqueous dispersion of the dimer acid polyamide resin will be described. As described above, the adhesive layer in the laminate of the present invention is preferably an aqueous dispersion in which a dimer acid-based polyamide resin is dispersed in an aqueous medium from the viewpoint of work environment, but is not limited thereto. .
In obtaining an aqueous dispersion of a dimer acid-based polyamide resin, it is preferable to use a sealable container. That is, a means for preparing each component in a sealable container, heating and stirring is preferably employed.
Specifically, first, a predetermined amount of dimer acid-based polyamide resin, a basic compound, and an aqueous medium are put into a container. As described above, since the basic compound or the hydrophilic organic solvent described later may be contained in the aqueous medium, for example, if an aqueous medium containing the basic compound is used, the basic compound is separately provided. As a result, the basic compound is charged into the container.
Next, the container is sealed, and heated and stirred at a temperature of preferably 70 to 280 ° C, more preferably 100 to 250 ° C. When the temperature at the time of heating and stirring is less than 70 ° C., the dispersion of the dimer acid-based polyamide resin is difficult to proceed and the number average particle diameter of the resin tends to be difficult to be 0.5 μm or less, whereas it exceeds 280 ° C. In some cases, the molecular weight of the dimer acid-based polyamide resin may decrease, and the internal pressure of the system may increase to a level that cannot be ignored.
When heating and stirring, it is preferable to heat and stir at 10 to 1000 revolutions per minute until the resin is uniformly dispersed in the aqueous medium.

Further, a hydrophilic organic solvent may be added to the container. In this case, the hydrophilic organic solvent has a solubility in water at 20 ° C. from the viewpoint of further reducing the particle size of the dimer acid-based polyamide resin and further promoting the dispersion of the dimer acid-based polyamide resin in the aqueous medium. Preferably, a hydrophilic organic solvent that is soluble in an arbitrary ratio with water may be selected and used, preferably 50 g / L or more, more preferably 100 g / L or more, further preferably 600 g / L or more. Moreover, as a boiling point of a hydrophilic organic solvent, it is preferable that it is 30-250 degreeC, and it is more preferable that it is 50-200 degreeC. When the boiling point is less than 30 ° C., the hydrophilic organic solvent is likely to volatilize during the preparation of the aqueous dispersion. As a result, the meaning of using the hydrophilic organic solvent is lost and the working environment is also liable to be lowered. On the other hand, when it exceeds 250 ° C., it tends to be difficult to remove the hydrophilic organic solvent from the aqueous dispersion. As a result, when the coating film is formed, the organic solvent remains in the coating film, May reduce solvent resistance.
As in the case of the basic compound described above, a hydrophilic organic solvent may be contained in the aqueous medium, so if an aqueous medium containing a hydrophilic organic solvent is used, an additional hydrophilic organic solvent is added separately. Even if not, as a result, the hydrophilic organic solvent is charged in the container.

  The blending amount of the hydrophilic organic solvent is preferably 60% by mass or less based on the total of the components constituting the aqueous medium (water, basic compounds and various organic solvents including the hydrophilic organic solvent). 1-50 mass% is more preferable, 2-40 mass% is further more preferable, and 3-30 mass% is especially preferable. When the blending amount of the hydrophilic organic solvent exceeds 60% by mass, not only the effect of promoting aqueous formation can be expected, but also the aqueous dispersion tends to gel in some cases, such being undesirable.

  Specific examples of the hydrophilic organic solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-amyl alcohol, isoamyl alcohol, sec-amyl alcohol, tert- Alcohols such as amyl alcohol, 1-ethyl-1-propanol, 2-methyl-1-butanol, n-hexanol, cyclohexanol; ketones such as methyl ethyl ketone, methyl isobutyl ketone, ethyl butyl ketone, cyclohexanone, isophorone; tetrahydrofuran, Ethers such as dioxane; ethyl acetate, acetic acid-n-propyl, isopropyl acetate, acetic acid-n-butyl, isobutyl acetate, acetic acid-sec-butyl, acetic acid-3-methoxybutyl, Esters such as methyl lopionate, ethyl propionate, diethyl carbonate, dimethyl carbonate; ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol ethyl ether acetate, diethylene glycol Glycol derivatives such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol ethyl ether acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol methyl ether acetate; 3-methoxy-3-methylbutanol, 3-methoxybutanol, acetonitrile, dimethylformamide, dimethylacetamide, diacetone alcohol, and the like ethyl acetoacetate.

  A part of the organic solvent or basic compound blended at the time of aqueous formation can be removed from the aqueous dispersion by a solvent removal operation called stripping. By such stripping, the content of the organic solvent can be reduced to 0.1% by mass or less as necessary. Even if the content of the organic solvent is 0.1% by mass or less, the influence on the performance of the aqueous dispersion is not particularly confirmed. Examples of the stripping method include a method in which the aqueous dispersion is heated with stirring at normal pressure or reduced pressure to distill off the organic solvent. At this time, it is preferable to select a temperature and pressure at which the basic compound is not completely distilled off. Moreover, since a solid content concentration in an aqueous dispersion becomes high when a part of aqueous medium is distilled off simultaneously, it is preferable to adjust the solid content concentration appropriately.

  Examples of hydrophilic organic solvents that can be easily removed include, for example, ethanol, n-propanol, isopropanol, n-butanol, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, dioxane, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol mono Examples thereof include butyl ether, and ethanol, n-propanol, isopropanol, tetrahydrofuran and the like are particularly preferably used in the present invention. A hydrophilic organic solvent that can be easily removed from the solvent is preferably used in the present invention because it generally contributes to the promotion of water-based resin.

  Further, when obtaining an aqueous dispersion, for the purpose of promoting the dispersion of the resin in the aqueous medium containing the hydrophilic organic solvent, a hydrocarbon-based organic solvent such as toluene or cyclohexane is added to the entire components constituting the aqueous medium. You may mix | blend in 10 mass% or less of range. If the blending amount of the hydrocarbon-based organic solvent exceeds 10% by mass, separation from water becomes significant in the production process, and a uniform aqueous dispersion may not be obtained.

The aqueous dispersion of the dimer acid-based polyamide resin can be obtained by the above method, but after each component is heated and stirred, the obtained aqueous dispersion may be cooled to room temperature as necessary. Of course, the aqueous dispersion does not aggregate at all even through such a cooling process, and the stability is naturally maintained.
And after cooling an aqueous dispersion, even if this is immediately paid out and it uses for the next process, there is basically no problem. However, since a foreign substance and a small amount of undispersed resin may rarely remain in the container, it is preferable to provide a filtration step once before discharging the aqueous dispersion. Although it does not specifically limit as a filtration process, For example, the means of carrying out pressure filtration (for example, air pressure 0.5MPa) with a 300 mesh stainless steel filter (wire diameter 0.035mm, plain weave) is employable.
After obtaining an aqueous dispersion of a dimer acid-based polyamide resin, an aqueous coating agent for forming an adhesive layer can be obtained by mixing an appropriate amount of this aqueous dispersion and a dispersion or solution containing a crosslinking agent.

  On the other hand, when the dimer acid-based polyamide resin is dissolved in an aqueous medium to form an aqueous coating material, for example, the polyamide resin is added to a hydrophilic organic solvent such as n-propanol and heated at a temperature of 30 to 100 ° C. After the resin is once dissolved by stirring, an aqueous coating agent for forming an adhesive layer can be obtained by adding an appropriate amount of a dispersion or solution containing water and the above-mentioned crosslinking agent.

The adhesive layer-forming coating agent is preferably an aqueous coating agent as described above, but may be one in which a dimer acid-based polyamide resin and a crosslinking agent are dispersed or dissolved in an organic solvent.
Examples of the organic solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-amyl alcohol, isoamyl alcohol, sec-amyl alcohol, tert-amyl alcohol, 1- Alcohols such as ethyl-1-propanol, 2-methyl-1-butanol, n-hexanol and cyclohexanol; ketones such as methyl ethyl ketone, methyl isobutyl ketone, ethyl butyl ketone, cyclohexanone and isophorone; ethers such as tetrahydrofuran and dioxane Ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, 3-methoxybutyl acetate, mepionate , Esters such as ethyl propionate, diethyl carbonate, dimethyl carbonate; ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol ethyl ether acetate, diethylene glycol, diethylene glycol Glycol derivatives such as monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol ethyl ether acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol methyl ether acetate; Examples include -3-methylbutanol, 3-methoxybutanol, acetonitrile, dimethylformamide, dimethylacetamide, diacetone alcohol, ethyl acetoacetate, toluene, xylene, and cyclohexane. If necessary, these organic solvents can be mixed and used. May be.

  The content (solid content concentration) of the dimer acid-based polyamide resin in the adhesive layer-forming coating material can be appropriately selected according to the purpose of use and the storage method, and is not particularly limited, but is preferably 3 to 40% by mass. Of these, the content is preferably 10 to 35% by mass. If the content of the dimer acid polyamide resin in the adhesive layer forming coating is less than the above range, it may take time to form the coating film by the drying process, and it tends to be difficult to obtain a thick coating film. It is in. On the other hand, when the content of the dimer acid-based polyamide resin in the coating for forming an adhesive layer is more than the above range, the coating tends to have low storage stability.

  The viscosity of the adhesive layer-forming coating material is not particularly limited, but it is preferably low viscosity even at room temperature. Specifically, the rotational viscosity measured at 20 ° C. using a B-type viscometer (manufactured by Tokimec, DVL-BII type digital viscometer) is preferably 20000 mPa · s or less, more preferably 5000 mPa · s or less, More preferably 500 mPa · s or less. When the viscosity of the adhesive layer-forming coating agent exceeds 20000 mPa · s, it tends to be difficult to uniformly apply the coating agent to the resin film.

  Depending on the application, the adhesive layer-forming coating may be an antistatic agent, leveling agent, UV absorber, antifoaming agent, thickener, wax, anti-skinning agent, matting agent, inorganic or organic particles. Additives such as lubricants may be blended, and good dispersion stability is maintained even when a basic material is blended as the additive.

  In particular, the adhesive layer formed by applying a coating for forming an adhesive layer to which inorganic or organic particles have been added to the surface of the resin film and drying it is easy to slip and block resistance when the laminate is wound up once. Is preferable. Examples of inorganic particles to be added include silica, colloidal silica, alumina, alumina sol, tin oxide, titanium oxide, zinc oxide, niobium oxide, neodymium oxide, lanthanum oxide, zirconium oxide, cerium oxide, magnesium oxide, and the like. Polyethylene, polypropylene, styrene, silicone, nylon, acrylic, polyacrylonitrile, benzoguanamine / formaldehyde condensate, melamine / formaldehyde condensate, styrene divinylbenzene, acrylic divinylbenzene, and the like.

(Formation of adhesive layer)
As a method of providing an adhesive layer on the above-mentioned resin film, a method of applying the above-mentioned adhesive layer forming coating agent to a biaxially stretched resin film (offline method), an adhesive layer to a resin film before biaxial stretching A method (in-line method) of stretching and heat treatment after applying the coating agent for formation can be mentioned, and any method can be adopted. In addition, a method of providing an adhesive layer by bonding a substrate provided with an adhesive layer to a substrate to be adhered to a resin film, or a resin obtained by forming an adhesive layer on a substrate film such as a release film It is also possible to adopt a method such as transferring the adhesive layer by peeling the release film after bonding to the film.

By applying the adhesive layer forming coating agent during the resin film manufacturing process as described above, the adhesive layer forming coating agent can be applied in a state where the degree of orientation crystallization on the resin film surface is small. Adhesion between the resin film and the adhesive layer is improved. Moreover, adhesiveness of the adhesive layer can be improved without lowering the quality of the resin film by performing higher temperature heat treatment on the adhesive layer in a state where the resin film is in tension. The heat treatment temperature can be 250 ° C. or higher, which is the heat setting temperature of the resin film, and orientation crystallization proceeds in the adhesive layer together with the resin film at this temperature. In addition, in the formed adhesive layer, the dimer acid-based polyamide resin and the cross-linking agent sufficiently react, and the adhesive layer is expected to increase the coating strength of itself and to increase the adhesion to the resin film.
Furthermore, the in-line method of applying the adhesive layer forming coating during the resin film manufacturing process not only simplifies the manufacturing process compared to off-line coating, but also reduces the cost of the adhesive layer. This is also advantageous.

When the simultaneous biaxial stretching method is adopted in the production of the resin film, the adhesive layer-forming coating agent is applied to the unstretched film, dried, and then 50 ° C. higher than the Tg to Tg of the resin constituting the resin film. In this range, biaxial stretching is performed so that the stretching ratio is about 2 to 4 times in the longitudinal and width directions. Prior to guiding to the simultaneous biaxial stretching machine, preliminary longitudinal stretching of about 1 to 1.2 times may be performed.
In addition, when adopting the sequential biaxial stretching method, the adhesive film forming coating agent is applied to the resin film stretched in the uniaxial direction, and then the resin film is further stretched in the direction perpendicular to the direction. However, it is preferable for reasons of simplicity and operation.

  As a method of applying the adhesive layer forming coating agent to the resin film, a known method can be adopted. For example, gravure roll coating, reverse roll coating, wire bar coating, lip coating, air knife coating, curtain flow coating, spray coating, dip coating, brush coating, etc. can be employed. By these methods, it can apply | coat uniformly on the surface of a resin film.

  After applying the adhesive layer-forming coating agent to the resin film, the aqueous medium can be removed by drying and heat treatment to obtain a laminate in which the adhesive layer composed of a dense coating film is adhered to the resin film. it can.

<Use of laminate>
The laminate of the present invention is composed of an adhesive layer containing a dimer acid-based polyamide resin and a crosslinking agent, and a specific resin film, and thus has transparency and excellent adhesion between the resin film and the adhesive layer. In addition, the adhesive layer is excellent in adhesion to the adherend even in a short manufacturing process. Therefore, the laminate of the present invention can be used as a single-sided adhesive sheet for adhesion to an adherend or as a double-sided adhesive sheet for adhesion between adherends, and the laminate and the adherend are bonded. Articles can be manufactured.
The method for adhering the laminate of the present invention and the adherend is not particularly limited, but specifically, a method of laminating by hot pressing, a method of laminating and extruding a resin on the laminate, and laminating Examples thereof include a method of coating on the body and a method of forming a film by vapor deposition.

In the case of bonding by hot pressing, the adhesive layer in the present invention contains dimer acid polyamide resin, so that the thermal pressing conditions such as temperature, pressure, time, etc. are milder than those of the adhesive layer containing thermosetting resin. It can be. The hot press is preferably higher than the softening point of the resin, particularly preferably 180 ° C or higher, and more preferably 180 to 200 ° C. The hot pressing time is preferably about 1 to 120 minutes, more preferably 3 to 60 minutes, and even more preferably 5 to 30 minutes. For example, when an epoxy resin is used as an adhesive, heat pressing is performed at 200 ° C. for 2 hours. By using a dimer acid polyamide resin, the heat pressing condition is 180 ° C. for 15 minutes. The temperature can be lowered and shortened. However, the hot press conditions can be changed and selected in various ways depending on the characteristics required for the metal plate to be used, the type of adhesive layer, the type of resin layer, the type of hot press machine, the combination of capabilities, or the resulting laminate. This is not the case.
The adherend used for bonding by hot pressing is not particularly limited, and examples thereof include metals, resins, and ceramics.
Metals include copper, tin, aluminum, lead, brass, zinc, silver, chromium, titanium, platinum, gallium, indium, antimony, molybdenum, cobalt, palladium, tungsten, germanium, antimony, and mixtures, compounds, alloys, etc. Is mentioned.
The thickness of the metal plate is not particularly limited.
The shape of the metal is not particularly limited, and may be any shape such as a plate shape, a rod shape, a wire shape, a tube shape, a foil top, and a block shape.
The metal forming method is not particularly limited, and can be formed by various methods such as casting, plastic working, sheet metal forming, cutting, cold forging, pressing, drawing, extrusion, and threading. is there. In addition, a surface having a mirror surface or a rough surface can be used by performing surface treatment such as machining, lathing, threading, grinding, and file processing. The surface may be subjected to treatments such as plating, thermal spraying, oxidation, rust prevention, quenching, painting, and coating.
Examples of resins include polyethylene, polystyrene, polypropylene, polycarbonate, polyamide, polyurethane, polymethyl methacrylate, polyethylene terephthalate, polyacetal, polyvinyl chloride, polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate, polyamideimide, polyetherimide, polyimide, Examples include polyether ether ketone, liquid crystal polymer, polytetrafluoroethylene, and polyvinylidene fluoride.
Examples of the ceramic include alumina, aluminum nitride, silicon nitride, steatite, sialon, zirconia, silicon carbide, forsterite, and cordierite. The ceramic is not particularly limited. Specifically, barium titanate, boron nitride, lead zirconate titanate, ferrite, alumina, forsterite, zircon, mullite, steatite, cordierite, silicon carbide, silicon nitride. , Aluminum nitride, steatite, zinc oxide, zirconia, sialon, silicon carbide, forsterite, cordierite, yttrium-based superconductor, bismuth-based superconductor, and the like.

  Examples of the adherend of the laminated body in which the resin is melt-extruded and bonded together include the above-described resins.

  Examples of the adherend formed by coating or vapor deposition on the laminate using the adhesive layer of the present invention as a primer layer include a hard coat layer, a printing layer, an adhesive layer, a release layer, an antistatic layer, Examples of the functional layer include a conductive layer, a barrier layer, a hydrophilic layer, a water repellent layer, an oil repellent layer, an ultraviolet absorbing layer, an infrared absorbing layer, and an antireflection layer.

As the hard coat layer, any conventionally used hard coat layer can be laminated, and it is preferable to laminate a layer mainly composed of a curable resin having chemical resistance and / or scratch resistance. .
Examples of the curable resin include an ionizing radiation curable resin, a thermosetting resin, and a thermoplastic resin. The layer forming operation for the resin film provided with the adhesive layer is easy, and the pencil hardness is easily set to a desired value. Therefore, ionizing radiation curable resins are preferable.
Specific examples of the curable resin used for forming the hard coat layer include, for example, acrylic resins, silicone resins, melamine resins, epoxy resins, urethane resins, and the like. From the viewpoint of further reduction of precipitated oligomers, further reduction of interference spots, and adhesion to the hard coat layer and the resin film, acrylic resins and silicone resins are preferable, and acrylic resins are more preferable.

The acrylic resin preferably has an acrylate functional group such as an acryloyl group and a methacryloyl group, and particularly preferably a polyester acrylate or a urethane acrylate. The polyester acrylate may be a (poly) acrylate of a polyester polyol oligomer. The urethane acrylate may be a (meth) acrylate of a urethane oligomer composed of a polyol compound and a polyisocyanate compound.
In addition, as a monomer for forming (meth) acrylate constituting polyester acrylate or urethane acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2 ethylhexyl (meth) acrylate, methoxy Examples include ethyl (meth) acrylate, butoxyethyl (meth) acrylate, and phenyl (meth) acrylate.

  Examples of the oligomer of polyester polyol constituting the polyester acrylate include aliphatic dicarboxylic acid such as adipic acid and glycol (for example, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, butylene glycol, polybutylene glycol, etc.) and / or triol. Products such as glycerin, trimethylolpropane and the like (eg, polyadipate triol), and aliphatic dicarboxylic acids such as sebacic acid and glycol (specific examples are the same as those described above) and / or triols (specific examples are Examples thereof include condensation products (for example, polysebacate polyol) and the like. In addition, you may substitute a part or all of the said aliphatic dicarboxylic acid with another organic acid. In this case, as the other organic acid, isophthalic acid, terephthalic acid, phthalic anhydride, or the like is preferable because high hardness is expressed in the hard coat layer.

The polyurethane oligomer constituting the urethane acrylate can be obtained from a condensation product of a polyisocyanate compound and a polyol compound.
Specific polyisocyanate compounds include adducts of methylene bis (p-phenylene diisocyanate), hexamethylene diisocyanate / hexane triol, hexamethylene diisocyanate, tolylene diisocyanate, tolylene diisocyanate trimethylolpropane, 1,5 Examples include naphthylene diisocyanate, thiopropyl diisocyanate, ethylbenzene-2,4-diisocyanate, 2,4-tolylene diisocyanate dimer, hydrogenated xylylene diisocyanate, and tris (4-phenyl isocyanate) thiophosphate.
Specific examples of the polyol compound include polyether polyols such as polyoxytetramethylene glycol, polyester polyols such as polyadipate polyol and polycarbonate polyol, and copolymers of acrylic acid esters and hydroxyethyl methacrylate.

  In order to further increase the hardness of the hard coat layer, a polyfunctional monomer can be used in combination with polyester acrylate or urethane acrylate. Specific polyfunctional monomers include, for example, trimethylolpropane tri (meth) acrylate, hexanediol di (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, pentaerythritol tri (meth) Examples include acrylate, dipentaerythritol hexa (meth) acrylate, 1,6 hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and the like.

  When the ionizing radiation curable resin is used as an ultraviolet curable resin, an acetophenone, benzophenone, mifilabenzoylbenzoate, α-amyloxime ester or thioxanthone is used as a photopolymerization initiator in these resins. In addition, it is preferable to use n-butylamine, triethylamine, tri-n-butylphosphine or the like as a photosensitizer.

Urethane acrylate is preferable from the viewpoint that the hard coat layer is rich in elasticity and flexibility and excellent in workability (foldability).
Polyester acrylate is preferable from the viewpoint that a hard coat layer with extremely high hardness can be formed by selecting the constituent components of the polyester.
Therefore, since it is easy to achieve both high hardness and flexibility, when the total amount of the acrylic resin is 100 parts by mass, acrylic mixed with 60 to 90 parts by mass of urethane acrylate and 40 to 10 parts by mass of polyester acrylate. A hard coat layer formed from a resin is preferred.

  Acrylic resins are available as commercial products. For example, Seika Beam series manufactured by Dainichi Seika Co., Ltd., Opstar series manufactured by JSR, UV curable hard coat agent purple light series manufactured by Nippon Synthetic Chemical Industry, UV manufactured by Yokohama Rubber Co., Ltd. Curing type hard coating agent HR320 series, HR330 series, HR350 series, HR360 series, UV curing type functional hard coating agent Lioduras / LCH series manufactured by Toyo Ink Co., Ltd. can be used. Acrylic resins may be used alone or in combination.

  The silicone-based resin may be one in which an acrylic group is covalently bonded to the silicone resin, or includes a condensate having a silanol group obtained by hydrolytic polycondensation of alkoxysilane. There may be. In particular, in the latter case, a silanol group is converted into a siloxane bond by heat curing after coating, and a hard coat layer is obtained as a cured film.

  Silicone resins are commercially available, for example, UV curable silicone hard coat agent X-12 series manufactured by Shin-Etsu Chemical Co., Ltd., UV curable silicone hard coat agent UVHC series manufactured by Momentive Performance Materials Japan, Inc. A thermosetting silicone hard coat agent SHC series, a UV curable functional hard coat agent Lipdiras · S series manufactured by Toyo Ink, Inc. can be used. Silicone resins may be used alone or in combination.

  The pencil hardness of the hard coat layer may vary depending on the application, and is usually HB or higher, preferably H or higher, more preferably 2H or higher. By having a hard coat layer, the resin film has improved scratch resistance and can be used in various applications. The hardness can be controlled by selecting the thickness, material, curing conditions and the like of the hard coat layer.

  Although the thickness of a hard-coat layer is not specifically limited, It is preferable to adjust in the range which does not impair an optical characteristic, and the range of 1-15 micrometers is preferable.

  The hard coat film is required to have excellent transparency in various uses such as a large display such as a television and a small display such as a mobile phone, a personal computer, and a smartphone. Usually, the transparency of a film is represented by haze and total light transmittance. The hard coat film obtained by laminating the above hard coat layer on the laminate of the present invention preferably has a haze of 5.0% or less, more preferably 4.0% or less, and even more preferably 3.5%. The total light transmittance is preferably 80% or more, more preferably 85%, and still more preferably 90% or more.

  Examples of the method for forming the hard coat layer include a method in which a hard coat layer forming coating solution is applied and cured on an adhesive layer laminated on a resin film.

  The coating liquid for forming a hard coat layer usually contains the above-described curable resin, and may contain additives such as an ultraviolet absorber, a leveling agent, an antifoaming agent, and an antioxidant as desired.

  As the coating liquid for forming the hard coat layer, a monomer or oligomer for forming the curable resin described above dissolved in a solvent or a solution dispersed in water may be used, or a liquid monomer or oligomer may be used. May be used as they are. As the solvent for dissolving the monomer or oligomer for forming the curable resin, the organic solvent exemplified in the production of the easy-adhesion layer-forming coating material can be used. Moreover, when making it disperse | distribute to water, you may use the above-mentioned emulsifier component which illustrated the coating agent for easily bonding layer formation in manufacture.

  As a method for applying the hard coat layer forming coating solution to the easy-adhesion layer, a known method can be employed. For example, gravure roll coating, reverse roll coating, wire bar coating, lip coating, air knife coating, curtain flow coating, spray coating, dip coating, brush coating, etc. can be employed. By these methods, it can apply | coat uniformly on the surface of an easily bonding layer.

  After applying the coating liquid for forming the hard coat layer to the adhesive layer, depending on the type of curable resin, the resin can be cured sufficiently by employing a method of irradiating ionizing radiation such as ultraviolet rays, a method of heating, etc. A hard coat layer can be formed on the easy adhesion layer laminated on the film.

  The printed layer is a layer having a colored pigment and / or dye and a binder (also referred to as a vehicle), and includes a stabilizer, a light stabilizer, a curing agent, a crosslinking agent, a plasticizer, an antioxidant, an ultraviolet absorber, a lubricant, Additives such as antistatic agents, fillers, etc. may be added as necessary. Binders include rosin, rosin ester, rosin modified resin, shellac, alkyd resin, phenolic resin, polyacetic acid resin, polystyrene resin, polyvinyl butyral resin, acrylic or methacrylic resin, polyamide resin, polyester resin, polyurethane Resin, epoxy resin, urea resin, melamine resin, aminoalkyd resin, nitrified cotton, nitrocellulose, ethyl cellulose, chlorinated rubber, cyclized rubber, linseed oil, cutting oil, soybean oil, hydrocarbon oil, etc. .

  The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer may be a pressure-sensitive adhesive usually used for pressure-sensitive adhesive tapes, and examples thereof include a rubber-based pressure-sensitive adhesive, an acrylic pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, and a urethane-based pressure-sensitive adhesive. In particular, an acrylic pressure-sensitive adhesive and a silicone pressure-sensitive adhesive excellent in adhesiveness and heat resistance are preferable. You may mix | blend a tack fire, antioxidant, and another additive with respect to said adhesive.

  The release agent constituting the release layer may be any release agent that is usually used for release films, and examples thereof include silicone resins, fluororesins, long-chain alkyl polymers, waxes, and olefin resins. The release layer may contain an additive such as a peel strength adjusting agent or oil.

  The material constituting the antistatic layer and the conductive layer may be any material that is usually used as an antistatic film or a conductive film. For example, indium doped oxide, antimony doped tin oxide, tin oxide, indium oxide, zinc oxide And conductive metal oxides such as polyaniline, polypyrrole, polythiophene, conductive carbon such as carbon black and ketjen black, metals such as silver, copper, and aluminum, and surfactants. . In addition to the above, a resin component or the like may be included as a binder.

  The material constituting the barrier layer may be any material that is normally used as a barrier film, such as a soft metal foil such as aluminum foil, or a vapor deposition layer such as aluminum vapor deposition, silica vapor deposition, alumina vapor deposition, or silica alumina binary vapor deposition. Examples thereof include organic barrier layers made of vinylidene chloride resin, modified polyvinyl alcohol, ethylene vinyl alcohol copolymer, MXD nylon and the like.

  The material constituting the hydrophilic layer may be any material that is normally used as a hydrophilic film, such as those using a hydrophilic polymer such as a polymer in which a hydrophilic functional group is added to polyvinyl alcohol, polyethylene glycol, acrylic, or the like. , Surfactants, inorganic materials such as silica, and the like.

  The material constituting the water-repellent layer and the oil-repellent layer may be any material that is usually used as a water-repellent / oil-repellent film, and examples thereof include fluororesin, wax, and silicone.

  The material constituting the ultraviolet absorbing layer may be any material that is usually used as an ultraviolet absorber, and organic materials such as benzophenone, benzotriazole, triazine, cyanoacrylate, oxalinide, salicylate, formamidine, and the like. System ultraviolet absorbers and the like. In addition to this, an ultraviolet reflector such as titanium oxide or zinc oxide, a radical scavenger such as a hindered amine, or the like may be added.

  The material constituting the infrared absorbing layer may be any material that is normally used as an infrared absorbing agent, such as lanthanum hexaboride, cesium tungsten oxide, cyanine dye, phthalocyanine dye, naphthalocyanine compound, nickel dithiolene complex, squalium dye. Quinone compounds, diimmonium compounds, azo compounds and the like.

  The material constituting the antireflection layer may be any material that is usually used as an antireflection film, and examples thereof include inorganic particles such as silica and organic particles such as styrene and acrylic. In addition to these, components such as a binder may be included.

Since the laminated body of this invention is excellent in adhesiveness with various to-be-adhered bodies, it can expand | deploy to various uses.
For example, an article in which a metal is bonded to the laminate of the present invention can be applied to a flexible blind substrate, a sensor component, and the like. In addition, the article to which the hard coat layer is bonded has excellent adhesion between the resin film and the adhesive layer, and the adhesion between the adhesive layer and the hard coat layer is excellent even in a moist heat environment, and is transparent and flexible. In addition, since it has a hard coat layer that prevents scratches, it can be used for flexible display applications using organic EL of next-generation display panels.
In addition, by adhering various adherends and functional layers to the laminate of the present invention, pharmaceutical packaging materials, food packaging materials such as retort foods, electronic component packaging materials for semiconductor packages, motors, transformers, cables Electrical insulation materials for capacitor materials, derivative materials for capacitor applications, cassette tapes, magnetic tapes for data storage for digital data storage, magnetic tape materials such as video tapes, solar cell substrates, liquid crystal plates, conductive films, organic LEDs Films mounted on sensors, protective plates for display devices, LED mounting substrates, flexible printed wiring boards, flexible flat cable and other electronic board materials, flexible printed wiring coverlay films, heat-resistant masking tapes, industrial tapes, etc. Heat-resistant adhesive tape, heat-resistant bar code label, heat-resistant Suitable for use as films for household and industrial materials such as reflectors, various release films, heat-resistant adhesive base films, photographic films, molding materials, agricultural materials, medical materials, civil engineering, building materials, filtration membranes, etc. Is possible.

Hereinafter, the present invention will be described specifically by way of examples. In addition, measurement and evaluation of various values in the examples were performed as follows.
(1) Dimer acid polyamide resin [acid value, amine value]
It was measured by the method described in JIS K 2501.

[Softening point temperature]
Using 10 mg of resin as a sample, using a microscope equipped with a microscope heating (cooling) apparatus heat stage (Heating-Freezing AGE TH-600, manufactured by Linkham Co., Ltd.), measurement was performed at a temperature rising rate of 20 ° C./min. The temperature at which the resin melted was defined as the softening point.

[Dimer acid content]
In tetrachloroethane (d ₂ ), ¹ H-NMR analysis (manufactured by Varian, 300 MHz) was performed at 120 ° C. to obtain.

(2) Aqueous dispersion [solid content concentration]
An appropriate amount of the obtained aqueous dispersion was weighed and heated at 150 ° C. until the mass of the residue (solid content) reached a constant weight, and the solid content concentration was determined.

[PH]
The pH was measured using a pH meter (Horiba, Ltd., F-52).

〔viscosity〕
A rotational viscosity (mPa · s) at a temperature of 25 ° C. was measured using a B-type viscometer (DVL-BII type digital viscometer manufactured by Tokimec).

[Number average particle diameter of resin]
The number average particle size of the resin in the aqueous dispersion was measured by a dynamic light scattering method using a Microtrac particle size distribution analyzer UPA150 (MODEL No. 9340) manufactured by Nikkiso Co., Ltd.

(3) Laminate [Adhesion]
About the adhesive layer of the laminated body produced in the Example, according to the method of JISK5600, it evaluated by the residual rate after cellophane tape peeling by the crosscut method. When considering the practical performance, it can be said that each adhesion has no problem if the residual ratio is 80% or more.

[Total light transmittance and haze]
The laminates obtained in the examples were measured according to JIS K 7136 using a turbidimeter (manufactured by Nippon Denka Kogyo Co., Ltd., “NDH2000”).

(4) Article with polyimide film adhered as adherend (4.1) Adhesiveness A measurement sample having a width of 25 mm and a length of 10 cm was cut out from the article prepared in the example and bonded with the polyimide film and pulled. Using a testing machine (precision universal material testing machine type 2020 manufactured by Intesco), the peel strength is measured by performing a T-type peel test at room temperature and under a pulling speed of 200 mm / min, and bonding is performed with the magnitude of the peel strength. Sex was evaluated. The measurement was performed at n = 5, and the average value was defined as the peel strength. The practical strength is preferably 4 N / 25 mm or more.

(4.2) Hot Adhesiveness A measurement sample having a width of 25 mm and a length of 10 cm was cut out from an article produced in the example and having a polyimide film adhered to a laminate, and a tensile tester (a precision universal material tester manufactured by Intesco). 2020) was used and the peel strength was measured by performing a T-type peel test under the conditions of 80 ° C. and a tensile speed of 200 mm / min, and the hot adhesiveness was evaluated based on the value. The measurement was performed at n = 3, and the average value was taken as the peel strength. In consideration of practical performance, the peel strength measured at 80 ° C. preferably has a maintenance rate of 60% or more of the peel strength measured in (4.1).

(4.3) Heat cycle resistance The article produced in the example and having the polyimide film adhered to the laminate was heated at −20 ° C. for 30 minutes, then to 150 ° C. over 2 hours, and then at 150 ° C. for 30 minutes. After the holding, the cycle of lowering the temperature to −20 ° C. again over 2 hours was defined as 1 cycle, and this was repeated 100 cycles.
Using a tensile tester (precision universal material testing machine type 2020 manufactured by Intesco), the peel strength was measured by performing a T-type peel test at room temperature and under a pulling speed of 200 mm / min. The heat cycle resistance was evaluated. In consideration of practical performance, it is preferable that the peel strength after the heat cycle has a maintenance rate of 50% or more of the peel strength measured in (4.1).

(5) Articles with a hard coat layer laminated as an adherend (hard coat film)
(5.1) Adhesiveness Regarding the adhesiveness between the resin film and the adhesive layer of the hard coat film produced in the examples, and the adhesiveness of the entire laminate after laminating the hard coat layer on the adhesive layer, JIS K According to the method described in 5600, the remaining rate after peeling of the cellophane tape was evaluated by a cross-cut method. When considering the practical performance, it can be said that each adhesion has no problem if the residual ratio is 85% or more.

(5.2) Moisture and heat resistance Regarding the heat and moisture resistance of the hard coat film between the resin film and the adhesive layer and the moisture and heat resistance of the adhesive layer and the hard coat layer, the laminate was 80 ° C. and 95% in a constant temperature and humidity chamber. After leaving in an RH environment for 48 hours, it was allowed to stand at room temperature and normal humidity for 12 hours, and adhesion was determined by the same method as in (5.1) above. In consideration of practical performance, it can be said that the adhesiveness is not a problem if the residual ratio is 85% or more.

(5.3) Flexibility Sample prepared by cutting a hard coat film (hereinafter, the surface on which the hard coat layer is formed is the front surface and the opposite side surface is the back surface) into a 30 mm × 100 mm rectangle. , A durability tester (DLDMMLH-FU, manufactured by Yuasa System Equipment Co., Ltd.) with a bending inner diameter of 5 mm, and a test for folding the entire surface of the sample by 180 degrees (a test for folding the back surface to be outside) 10000 The evaluation was performed as follows. In practice, evaluations A to C are required.
A: Up to 10,000 times, the sample did not have any fold marks, cracks, whitening, or peeling or floating of the hard coat layer.
B: The sample was not changed up to 5000 times, but by 10,000 times, any one of crease marks, cracks, whitening, peeling or floating of the hard coat layer occurred.
C: The sample did not change up to 1000 times, but by 5000 times, any one of crease marks, cracks, whitening, peeling off or floating of the hard coat layer occurred.
D: The sample was not changed up to 500 times, but by 1000 times, any of creases, cracks, whitening, peeling off or floating of the hard coat layer occurred.
E: There was no change in the sample at 250 times, but by 500 times, any one of crease marks, cracks, whitening, peeling of the hard coat layer and floating occurred.
F: The sample did not change after 100 times, but by 250 times, any of creases, cracks, whitening, peeling of the hard coat layer, and floating occurred.
G: Up to 100 times, fold marks, cracks, whitening, peeling or floating of the hard coat layer occurred.

(5.4) Total light transmittance and haze The hard coat film was measured according to JIS K 7136 using a turbidimeter (manufactured by Nippon Denka Kogyo Co., Ltd., “NDH2000”).

(5.5) Interference fringes A hard coat film is cut into an area of 10 cm × 15 cm, and a black glossy tape (made by Yamato, vinyl tape No. 200-5 black) on the surface opposite to the surface on which the hard coat layer is formed. , The hard coat surface as the upper surface, and a three-wavelength daylight white fluorescent lamp (National Purook, F.L15EX-N15W) as a light source, the reflected light was visually observed from obliquely upward at 30 to 60 °.
Good: No interference fringes are seen and the appearance is good.
Acceptable: Appearance of a level where there are slight interference fringes but no problem in practical use.
Not possible: Interference fringes are very conspicuous and the appearance is poor.

(5.6) Pencil Hardness About the hard coat film, pencil hardness was measured based on JIS K 5600-5-4 (1999) (1 kg load). In view of practical performance, the pencil hardness is desirably H or higher.

(5.7) Steel Wool Resistance A hard coat film is cut into an area of 10 cm × 15 cm, and the surface of the hard coat layer is 1 kg using # 0000 steel wool (trade name: BONSTAR, manufactured by Nippon Steel Wool Co., Ltd.). While applying a load of / cm ² , reciprocating friction was performed 3500 times at a speed of 50 mm / sec, and the number of scratches on the surface of the hard coat layer was visually confirmed. In consideration of practical performance, the number of scratches is preferably less than 20, more preferably less than 10.

(6) Articles laminated with metal plates as adherends (6.1) Peel strength (6.1.1) Peel strength before heat cycle test From metal plate laminate articles A and B produced in Examples and Comparative Examples A sample for measurement having a width of 25 mm and a length of 10 cm is cut out, and the surface of the metal plate is bonded and fixed to the stainless steel plate with a double-sided tape, a resin film is gripped, and a tensile tester (precision universal material testing machine 2020 manufactured by Intesco) is obtained. Mold), a T-type peel test was performed at room temperature and under a tensile speed of 200 mm / min, the peel strength was measured, and the adhesiveness was evaluated based on the value. Five measurement samples were collected, and the average value was defined as the peel strength before the heat cycle test.

(6.1.2) Peel strength after heat cycle test In addition, the metal plate laminate articles A and B were heated at −20 ° C. for 30 minutes, then heated to 150 ° C. over 2 hours, and then held at 150 ° C. for 30 minutes. After that, the cycle of lowering the temperature to −20 ° C. over 2 hours was taken as 1 cycle, and this was repeated 100 cycles. For the articles A and B after the heat cycle test, the peel strength was measured by the same method as described above, and the adhesion after the heat cycle test was evaluated. Practically, the peel strength is preferably 4 N / 25 mm or more before and after the heat cycle test.

(6.2) Appearance after heat test The articles A and B after the heat cycle test were further held at 260 ° C. for 15 minutes, and the subsequent appearance was visually confirmed according to the following criteria. This heat resistance test assumes a state in which the laminate of the present invention is actually used as a device part, particularly a state where it is used for reflow soldering.
Best: No blistering or peeling. In addition, no abnormal appearance is observed in the laminate.
Good: No swelling or peeling. However, some distortion is seen in the laminate.
Possible: Dandruff or peeling is seen.
Impossible: Both bulge and peeling are seen

The following P-1 to P-5 were used as the dimer acid-based polyamide resin, and P-6 was used as the polyolefin resin to produce aqueous dispersions.
[Dimer acid-based polyamide resin P-1]
The dicarboxylic acid component contains 100% by mole of dimer acid, and the diamine component contains 100% by mole of ethylenediamine. The acid value is 10.0 mgKOH / g, the amine value is 0.1 mgKOH / g, and the softening point is 158 ° C. Polyamide resin.

[Dimer acid-based polyamide resin P-2]
As dicarboxylic acid component, dimer acid is contained in 85 mol%, azelaic acid is contained in 15 mol%, piperazine is contained in 50 mol%, and ethylenediamine is contained in 50 mol%, and the acid value is 15.0 mgKOH / g and the amine value is Polyamide resin having 0.3 mg KOH / g and a softening point of 110 ° C.

[Dimer acid polyamide resin P-3]
The dicarboxylic acid component contains 100% by mole of dimer acid, the diamine component contains 100% by mole of ethylenediamine, the acid value is 20.3 mgKOH / g, the amine value is 0.1 mgKOH / g, and the softening point is 129 ° C. Polyamide resin.

[Dimer acid polyamide resin P-4]
The dicarboxylic acid component contains 60 mol% dimer acid, 40 mol% azelaic acid, the diamine component contains 50 mol% piperazine, 50 mol% ethylenediamine, the acid value is 10.5 mgKOH / g, and the amine value is Polyamide resin having 0.1 mg KOH / g and a softening point of 165 ° C.

[Dimer acid polyamide resin P-5]
Polyamide resin containing 100 mol% of dimer acid as dicarboxylic acid component, 100 mol% of ethylenediamine as diamine component, acid value 10.0 mgKOH / g, amine value 1.0 mgKOH / g, softening point 163 ° C .

[Polyolefin resin P-6]
As the polyolefin resin, “Bondyne LX4110” manufactured by Sumitomo Chemical Co., Ltd. was used.

[Production of Dimer Acid-Based Polyamide Resin Aqueous Dispersion E-1]
In a sealable pressure-resistant 1 liter glass container equipped with a stirrer and a heater, 75.0 g of dimer acid polyamide resin P-1, 37.5 g of isopropanol (IPA), 37.5 g of tetrahydrofuran (THF), 7.2 g Of N, N-dimethylethanolamine and 217.8 g of distilled water were charged. While stirring at a rotation speed of 300 rpm, the system was heated and stirred at 120 ° C. for 60 minutes. Thereafter, the mixture was cooled to around room temperature (about 30 ° C.) with stirring, 100 g of distilled water was added, and then filtered through a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave) with very slight pressure. The obtained aqueous dispersion was put into a 1 L eggplant flask and reduced in pressure using an evaporator while being put in a hot water bath heated to 80 ° C., and about 100 g of a mixed medium of IPA, THF, and water was distilled off to obtain a milky white uniform dimer acid. -Based polyamide resin aqueous dispersion E-1 was obtained. The solid content concentration of E-1 was 20% by mass, the number average particle size of the resin in the dispersion was 0.040 μm, the pH was 10.4, and the viscosity was 36 mPa · s.

[Production of Dimer Acid Polyamide Resin Aqueous Dispersion E-2]
In a sealable pressure-resistant 1 liter glass container equipped with a stirrer and a heater, 75.0 g of dimer acid-based polyamide resin P-2, 93.8 g of IPA, 6.0 g of N, N-dimethylethanolamine and 200.3 g Of distilled water. While stirring at a rotation speed of 300 rpm, the system was heated and stirred at 120 ° C. for 60 minutes. Thereafter, the mixture was cooled to around room temperature (about 30 ° C.) with stirring, 130 g of distilled water was added, and then filtered with a 300 mesh stainless steel filter (wire diameter: 0.035 mm, plain weave) with very slight pressure. The obtained aqueous dispersion was put into a 1 L eggplant flask and reduced in pressure using an evaporator while being put in a hot water bath heated to 80 ° C., and about 130 g of a mixed medium of IPA and water was distilled off to obtain a milky white uniform dimer acid polyamide. An aqueous resin dispersion E-2 was obtained. The solid content concentration of E-2 was 20% by mass, the number average particle size of the resin in the dispersion was 0.052 μm, the pH was 10.6, and the viscosity was 30 mPa · s.

[Production of Dimer Acid Polyamide Resin Aqueous Dispersion E-3]
In the production of the dimer acid-based polyamide resin aqueous dispersion E-1, a dimer acid-based polyamide resin aqueous dispersion E-3 was obtained by the same production method except that the resin P-1 was changed to the resin P-3. The solid content concentration of E-3 was 20% by mass, the number average particle size of the resin in the dispersion was 0.058 μm, the pH was 10.3, and the viscosity was 45 mPa · s.

[Production of Dimer Acid Polyamide Resin Aqueous Dispersion E-4]
In a sealable pressure-resistant 1 liter glass container equipped with a stirrer and a heater, 110.0 g of dimer acid-based polyamide resin P-4, 110.0 g of IPA, 110.0 g of THF, 9.2 g of N, N-dimethyl Ethanolamine, 11.0 g toluene, and 199.8 g distilled water were charged. While stirring at a rotation speed of 300 rpm, the system was heated and stirred at 120 ° C. for 60 minutes. Thereafter, the mixture was cooled to around room temperature (about 30 ° C.) with stirring, 330 g of distilled water was added, and the mixture was filtered with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave) with very slight pressure. The obtained aqueous dispersion was put into a 1 L eggplant flask and reduced in pressure using an evaporator while being put in a hot water bath heated to 80 ° C., and about 330 g of a mixed medium of IPA, THF, toluene and water was distilled off to obtain a milky white uniform Dimer acid-based polyamide resin aqueous dispersion E-4 was obtained. The solid content concentration of E-4 was 20% by mass, the number average particle size of the resin in the dispersion was 0.065 μm, the pH was 10.3, and the viscosity was 8 mPa · s.

[Dimer acid polyamide resin aqueous dispersion E-5]
75.0 g of dimer acid polyamide resin P-5, 37.5 g of IPA, 37.5 g of THF, 7.2 g of N, N-dimethylethanol in a hermetically sealed 1 liter glass container equipped with a stirrer and a heater The amine and 217.8 g of distilled water were charged. While stirring at a rotation speed of 300 rpm, the system was heated and stirred at 120 ° C. for 60 minutes. Thereafter, the mixture was cooled to around room temperature (about 30 ° C.) with stirring, 100 g of distilled water was added, and then filtered through a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave) with very slight pressure. The obtained aqueous dispersion was put into a 1 L eggplant flask, and reduced in pressure using an evaporator while being placed in a hot water bath heated to 80 ° C., and about 100 g of a mixed medium of IPA, THF, toluene, and water was distilled off to obtain a milky white uniform Dimer acid-based polyamide resin aqueous dispersion E-5 was obtained. The solid content concentration of E-5 was 20% by mass, the number average particle size of the resin in the dispersion was 0.045 μm, the pH was 10.6, and the viscosity was 5 mPa · s.

[Polyolefin resin aqueous dispersion N-1]
In a glass container with a pressure resistance of 1 liter which can be sealed with a stirrer and a heater, 60.0 g of polyolefin resin P-6, 28.0 g of IPA, 1.5 g of TEA and 210.5 g of distilled water are charged into the glass container. When the stirring blade was rotated at a rotational speed of 300 rpm, the resin bottoms were not observed at the bottom of the container, and it was confirmed that the container was in a floating state. Therefore, while maintaining this state, the heater was turned on and heated after 10 minutes. Then, the system temperature was kept at 140 ° C. and further stirred for 20 minutes. Then, after putting in a water bath and cooling to room temperature (about 25 ° C.) while stirring at a rotational speed of 300 rpm, pressure filtration (air pressure 0.2 MPa) with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave) Thus, a milky white uniform polyolefin resin aqueous dispersion N-1 was obtained.

The following were used for the resin which comprises a resin film, and the resin film.
[Semi-aromatic polyamide resin T-1]
1343 g of 1,9-nonanediamine (NMDA), 237 g of 2-methyl-1,8-octanediamine (MODA), 1627 g of terephthalic acid (TPA) (average particle size: 80 μm) (NMDA: MODA: TPA = 85: 15:99, molar ratio), 48.2 g of benzoic acid (BA) (4.0 mol% based on the total number of moles of dicarboxylic acid component and diamine component), 3.2 g of phosphorous acid (PA) (dicarboxylic acid component) And 1100 g of water with respect to the total amount of the diamine component) and 1100 g of water was put into the reactor and purged with nitrogen. Further, after stirring at 80 ° C. for 0.5 hour and 28 revolutions per minute, the temperature was raised to 230 ° C. Then, it heated at 230 degreeC for 3 hours. Thereafter, the mixture was cooled and the reaction product was taken out. After the reaction product was pulverized, it was heated in a dryer under a nitrogen stream at 220 ° C. for 5 hours and subjected to solid phase polymerization to obtain a polymer. And it melt-kneaded on the conditions of cylinder temperature 320 degreeC, and extruded in the shape of a strand. Then, it cooled and cut | disconnected and prepared the pellet-shaped semi-aromatic polyamide resin T-1.

[Semi-aromatic polyamide resin film F-1]
100 parts by weight of semi-aromatic polyamide resin T-1 and 0.2 parts by weight of 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane (GA) (manufactured by Sumitomo Chemical Co., Ltd., “Sumilyzer GA-80”, thermal decomposition temperature 392 ° C.) The molten polymer was obtained by charging into a single screw extruder having a screw diameter of 50 mm heated to 320 ° C. and melted. The molten polymer was filtered using a metal fiber sintered filter (manufactured by Nippon Seisen Co., Ltd., “NF-10”, absolute particle size: 30 μm). Then, it was extruded into a film form from a T die set at 320 ° C. to obtain a film-like melt. On the cooling roll set to 50 degreeC, this melt was closely_contact | adhered by the electrostatic application method, it cooled, and the substantially unoriented unstretched film (thickness: 250 micrometers) was obtained.
Next, while holding both ends of this unstretched film with clips, it was guided to a tenter type simultaneous biaxial stretching machine (inlet width: 193 mm, outlet width: 605 mm) to perform simultaneous biaxial stretching. The stretching conditions are as follows: the temperature of the preheating part is 120 ° C., the temperature of the stretching part is 130 ° C., the MD stretching strain rate is 2400% / min, the TD stretching strain rate is 2760% / min, and the MD stretching ratio is 3.0. The draw ratio of TD was 3.3 times.
Then, heat setting was performed at 270 ° C. in the same tenter, 5% relaxation treatment was applied in the width direction of the film, and biaxial stretching with a thickness of 25 μm, a haze of 4.2%, and a total light transmittance of 88.0%. A film was obtained.
The obtained biaxially stretched semi-aromatic polyamide resin film was used as the resin film F-1.

[Semi-aromatic polyamide resin film F-2]
A film was obtained by the same operation as the semi-aromatic polyamide resin film F-1, except that the semi-aromatic polyamide resin T-1 was changed to nylon 6T resin (Aren E, manufactured by Mitsui Chemicals). The obtained nylon 6T film was used as the resin film F-2.

[Polyimide resin film F-3]
As the resin film F-3, a polyimide film (Kapton 100H manufactured by Toray DuPont, thickness 25 μm) was used.

[Polyetherimide resin film F-4]
As the resin film F-4, a polyetherimide film (Mitsubishi Resin Super UT, thickness 25 μm) was used.

[Semi-aromatic polyamide resin film F-5]
The semiaromatic polyamide resin T-1 was changed to an aromatic nylon resin (Zecot XN500 manufactured by Unitika Ltd.), and a film was obtained by the same operation as the semiaromatic polyamide resin film F-1. The obtained aromatic nylon film was used as resin film F-5.

[Transparent polyimide resin film F-6]
A polyimide film (Neoprim L-3450 30 μm, haze 1.0%, total light transmittance 91.0%, manufactured by Mitsubishi Gas Co., Ltd.) was used as the resin film F-6.

[Polyethylene terephthalate resin film F-7]
As the resin film F-7, a polyethylene terephthalate film (Embret S-25 manufactured by Unitika Ltd., thickness 25 μm, haze 4.5%, total light transmittance 88%) was used.

[Nylon 6 resin film F-8]
As the resin film F-8, a nylon 6 film (Emblem ON-25 manufactured by Unitika Ltd., thickness 25 μm, haze 4.0%, total light transmittance 88%) was used.

[Nylon 6, 6 resin film F-9]
Semi-aromatic polyamide resin T-1 was changed to nylon 6,6 resin (UBE nylon 66 manufactured by Ube Industries), and a film was obtained by the same operation as semi-aromatic polyamide resin film F-1. The obtained nylon 6,6 film was used as the resin film F-9.

[Polyetheretherketone resin film F-10]
As the resin film F-10, a polyether ether ketone film (EXPEEK manufactured by Kurabo Industries, thickness 25 μm) was used.

Example 1
Dimer acid-based polyamide resin aqueous dispersion E-1 and an oxazoline group-containing polymer aqueous solution (Nippon Shokubai Co., Ltd., Epocros WS-700, solid concentration 25% by mass), each having a solid content of 100 parts by mass / 10 It mix | blended so that it might become the ratio of a mass part, and it stirred for 5 minutes at room temperature, and obtained the coating agent for contact bonding layer formation.
The obtained coating agent was dried and applied to a semi-aromatic polyamide resin film F-1 at a thickness of 3 μm and dried under conditions of 150 ° C. and 30 seconds to obtain a laminate.
(Adhesion of polyimide film)
A polyimide film (Kapton 100H, Toray DuPont Kapton 100H, thickness 25 μm) as an adherend is superimposed on the surface of the adhesive layer of the obtained laminate, and a heat press (sealing pressure 0.2 MPa, 200 ° C., 10 minutes) is used. An article was obtained by pressing to adhere a polyimide film to the laminate.
(Lamination of hard coat layer)
A coating liquid for forming a hard coat layer (acrylic hard coat resin (Seika Beam EXF01BPHC manufactured by Dainichi Seika Co., Ltd.)) is applied at a thickness of 3 μm after curing to the adhesive layer surface of the obtained laminate, and a low-pressure mercury lamp UV cure device ( Curing was performed with Toshiba Lighttech Co., Ltd. (40 mW / cm single lamp type) to obtain an article (hard coat film) in which a hard coat layer was laminated as an adherend on the laminate.
(Lamination of metal plates)
An electrolytic copper foil (made by Furukawa Electric Co., Ltd., surface CTS treatment, thickness 18 μm) as a metal plate is superimposed on the adhesive layer surface of the obtained laminate, and pressed with a heat press machine (180 ° C., 15 minutes, 2 MPa). Article A (180 ° C. × 15 min press product) composed of a metal plate, an adhesive layer and a resin film was obtained.
Moreover, it pressed with the heat press machine (200 degreeC, 120 minutes, 2 MPa), and obtained the article | item B (200 degreeCx120min press goods) comprised from the order of a metal plate, an adhesive layer, and a resin film.
In Example 1B, an aluminum foil (A1N30, 15 μm thickness, manufactured by Toyo Aluminum Co., Ltd.) was used as the metal plate. In Example 1C, a stainless steel foil (Nisshin Steel Co., Ltd., SUS-304-H-TA) was used. , Thickness 20 μm).

Examples 2 to 15 and Comparative Examples 1 to 9
The same procedure as in Example 1 was conducted except that the type of aqueous dispersion, the type and amount of solid content of the crosslinking agent, and the type of resin film were those shown in Table 1, and a coating agent for forming an adhesive, A laminate and article were obtained. In Examples 8 and 9, an epoxy group-containing polymer aqueous solution (manufactured by ADEKA, Adeka Resin EM-051R, solid content concentration 49.8% by mass) was used as the aqueous solution of the crosslinking agent. A carbodiimide group-containing polymer dispersion (manufactured by Nisshinbo Chemical Co., Ltd., Carbodilite series E-01, solid content concentration: 40% by mass) was used as a dispersion of the crosslinking agent.
In Comparative Example 8, an epoxy resin is used instead of the aqueous dispersion. Specifically, 100 parts of an epoxy resin (jER1001 manufactured by Mitsubishi Chemical Corporation) and diaminodiphenyl sulfone (Tokyo Chemical Industry) as a curing agent are used. 20 parts of Kogyo Kogyo Co., Ltd. were dissolved and decomposed in methyl ethyl ketone (Tokyo Kasei Kogyo Co., Ltd.) to obtain an adhesive having a concentration of 40%. In Comparative Example 9, a hot melt resin (STAYSTIK # 383 manufactured by Techno Alpha Co., Ltd.) was heated and then adjusted to a thickness of 15 μm, and a laminate was obtained in the same manner as in Example 1.

Example 16
The semi-aromatic polyamide resin T-1 was charged into a 65 mm single-screw extruder set at a cylinder temperature of 295 ° C. (front stage), 320 ° C. (middle stage), and 320 ° C. (rear stage), and melted to set to 320 ° C. Extruded into a film form from a T-die and cooled by pressing and adhering to a cooling roll with a circulating oil temperature set to 50 ° C. by an electrostatic application method to form a substantially non-oriented unstretched film A having a thickness of 240 μm Obtained. The cooling roll used was coated with ceramic _(Al 2 _{O 3)} to 0.15mm thickness on the surface. Further, two carbon brushes were arranged on the upstream side of the point where the roll surface and the film were in contact with each other and brought into contact with the cooling roll, and the surface of the ceramic coating layer was discharged by grounding the carbon brush holder. A tungsten wire having a diameter of 0.2 mm was used as an electrode, and a voltage of 6.5 kV was applied with a 300 W (15 kV × 20 mA) DC high voltage generator.
Next, after applying the adhesive layer-forming coating agent prepared by the method described in Example 1 to one side of the unstretched film A so as to be 8.0 g / m ² with a gravure roll, While holding both ends with clips, lead to a tenter type simultaneous biaxial stretching machine (manufactured by Hitachi, Ltd.), preheating temperature 125 ° C, stretching temperature 130 ° C, longitudinal stretching strain rate 2400% / min, transverse stretching strain rate Simultaneous biaxial stretching was performed at 2760% / min, a longitudinal stretching ratio of 3.0 times, and a transverse stretching ratio of 3.3 times. And after heat-fixing at 285 ° C. in the same tenter, giving a 5% relaxation treatment in the width direction of the film, cooling it uniformly, releasing both ends of the film from the clips, trimming the ears, A laminate having an adhesive layer having a thickness of 150 nm was obtained on a biaxially stretched semi-aromatic polyamide film having a width of 0.5 m and a length of 500 m.

Example 17
In the same manner as in Example 16, an unstretched film A was obtained. This unstretched film A was stretched 3.0 times with a roll-type longitudinal stretching machine at 105 ° C. to obtain a longitudinally stretched film B.
Next, the adhesive layer-forming coating agent prepared by the method described in Example 1 was applied to the surface of the longitudinally stretched film B so as to have a gravure roll of 6.0 g / m ^2, and then continuously the end of the film. The part is gripped by a clip of a flat type stretching machine, stretched 3.3 times in the transverse direction at 140 ° C, and then heat-fixed at 285 ° C with a lateral relaxation rate of 5%. A laminate having a thickness of 25 μm was obtained.

  The composition of the adhesive layer in the laminates of Examples and Comparative Examples, the types of resin films are shown in Table 1, the adhesion of the resulting laminates, the total light transmittance, the evaluation results of haze, and the adhesion to the laminates Table 2 shows the characteristics of an article to which a polyimide film is bonded as a body.

  As shown in Table 1, the laminates obtained in the examples were bonded to at least one surface of a film made of a semi-aromatic polyamide or a polyimide resin and composed of a dimer acid polyamide resin defined in the present invention and a crosslinking agent. As shown in Table 2, the resin film and the adhesive layer show good adhesion, and the article obtained by adhering the polyimide film to the adhesive layer of the laminate in a short thermocompression step is Good adhesion was exhibited at room temperature and at high temperatures. Among these, when the oxazoline compound was used as a crosslinking agent, the adhesiveness was the best.

On the other hand, the laminate (Comparative Example 1) containing no cross-linking agent in the adhesive layer has good adhesion between the adhesive layer and the resin film, but the polyimide film-adhered article has poor adhesion and heat resistance.
The laminate (Comparative Example 2) in which the amine value of the dimer acid-based polyamide resin in the adhesive layer exceeded the range defined in the present invention was poor in adhesiveness in the polyimide film adhesive article.
Moreover, when polyethylene terephthalate was used for resin which comprises a resin film (comparative example 3), it was inferior to heat resistance.
When nylon 6, nylon 6,6, or polyether ether ketone was used as the resin constituting the resin film (Comparative Examples 4, 5, and 6), the adhesion, adhesion, and heat resistance were poor.
A laminate (Comparative Example 7) provided with an adhesive layer using an aqueous dispersion of a polyolefin resin instead of a dimer acid-based polyamide resin was inferior in adhesiveness and heat resistance in a polyimide film adhesive article.
The laminate (Comparative Example 8) provided with an adhesive layer using an epoxy resin adhesive instead of the dimer acid polyamide resin was inferior in adhesion and adhesiveness.
The laminate (Comparative Example 9) provided with an adhesive layer using a hot melt resin instead of the dimer acid-based polyamide resin was inferior in adhesion, adhesiveness, and heat resistance.

  Table 3 shows the characteristics of the articles obtained by bonding the hard coat layer as the adherend to the laminates in Examples and Comparative Examples.

As shown in Table 3, the articles obtained by adhering the hard coat layer to the adhesive layers of the laminates of Examples 1, 3, 5 to 6, 15 and Examples 16 and 17 formed by the in-line method are bonded to the resin film. The layer and the entire laminate exhibited good adhesion, transparency and flex resistance were good, and the hard coat layer had good scratch resistance.
On the other hand, an article in which a hard coat layer is adhered to an adhesive layer of a laminate (Comparative Example 1) that does not contain a crosslinking agent in the adhesive layer is inferior in the adhesion of the entire laminate, and in the flex resistance test, Floating occurred and the bending resistance was poor.
In addition, when polyethylene terephthalate is used as the resin constituting the resin film (Comparative Example 3), the article with the hard coat layer adhered is inferior in bending resistance due to bending marks, cracking, and whitening in the bending resistance test. The stripes were very conspicuous and the appearance was poor.
When Nylon 6 is used as the resin constituting the resin film (Comparative Example 4), the adhesive layer is inferior in adhesion to the resin film, causing a gap between the resin film and the adhesive layer, and conducting a scratch resistance test. could not.

  Table 4 shows the characteristics of the articles obtained by bonding the metal plates as adherends to the laminates in the examples and comparative examples.

As shown in Table 4, the article A in which the metal plate was adhered to the adhesive layers of the laminates of Examples 1, 5, and 7 was the article B obtained by the thermocompression bonding process at a high temperature of 200 ° C. and 120 minutes for a long time. As is apparent from the comparison, excellent adhesiveness was exhibited even in a heat-pressing process at 180 ° C. for 15 minutes, and the adhesiveness was maintained even after the heat cycle test, and no blistering or peeling occurred. .
On the other hand, when the resin constituting the adhesive layer was a polyolefin resin (Comparative Example 7), the adhesiveness was inferior, and both blistering and peeling were observed in the article after the heat cycle test.
When the resin constituting the adhesive layer is an epoxy resin (Comparative Example 8), the article A having a low pressing temperature and a short pressing time when the metal plates are laminated has low adhesiveness, and blistering or peeling occurs after the heat cycle test. In addition, the article B having a higher pressing temperature and longer pressing time at the time of laminating metal plates did not cause swelling or peeling after the heat cycle test, but had low adhesion.
When the adhesive layer is a hot melt resin (Comparative Example 9), the peel strength cannot be measured because the adhesive layer has melted out of the laminate after the heat cycle test of the article A because the adhesive layer has low heat resistance. In the article after the heat cycle test, both blistering and peeling were observed. In addition, since the adhesive layer was melted from the laminate during the production of the article B with the press temperature increased and the press time increased, the peel strength could not be measured and the heat cycle test could be performed. There wasn't.

Claims (6)

A laminate in which an adhesive layer is provided on at least one surface of a resin film, and an article in which a hard coat layer is bonded ,
The resin constituting the resin film is a semi-aromatic polyamide and / or a polyimide resin,
Adhesive layer, amine value is characterized by containing a dimer acid-based polyamide resin is less than 1.0 mgKOH / g, a crosslinking agent article. The article according to claim 1, comprising 0.5 to 50 parts by mass of a crosslinking agent with respect to 100 parts by mass of the dimer acid-based polyamide resin. The article according to claim 1 or 2, wherein the crosslinking agent is an oxazoline compound. The article according to any one of claims 1 to 3, wherein the dimer acid-based polyamide resin has an acid value of 1 to 20 mgKOH / g. The article according to any one of claims 1 to 4, wherein the haze is 5.0% or less. The article according to any one of claims 1 to 5 , wherein the article is a flexible display article.