JP6034210B2 - Composition for substrate treatment, method for producing laminate substrate, and laminate substrate - Google Patents

Description

  The present invention relates to a composition for treating a substrate, a method for producing a laminated substrate, and a laminated substrate.

  Resin base materials (plastic films, plastic sheets, etc.) are used as materials for displays such as plasma displays (PDP) and liquid crystal displays (LCD), touch panel sheets, and icon sheets. Resin base material is lightweight and excellent in workability, but etching process etc. will also erode and damage the base material itself, which will impair optical properties, electrical properties, workability, etc. . Moreover, when using resin-made base materials as an optical material and electronic material as mentioned above, the improvement of the surface hardness of a base material is requested | required. For these reasons and the like, surface treatment of the base material is performed using a processing agent called a hard coat liquid.

  As a technique relating to such a treatment agent, Patent Document 1 includes a composition or a composition containing at least a monomer or oligomer containing acrylate as a main component, a polythiol compound having two or more thiol groups, and a photopolymerization initiator. The technique which forms a hard-coat layer by apply | coating to the film base material the hard-coat liquid whose ratio of the polythiol compound in the range of 5-50 mass%, drying and hardening is disclosed.

JP 2012-197383 A

  However, there is still room for improvement in conventional surface treatment techniques including Patent Document 1 and the like. For example, when the surface treatment of the substrate is performed using the above-described treatment agent, whitening, yellowing, spots, and the like are generated on the surface of the substrate, resulting in poor appearance. Such an appearance defect is not preferable in that it causes uneven interference of light and the like and impairs the optical characteristics of the optical material and the electronic material.

  Further, in order to maintain sufficient characteristics as a substrate even after performing the above-described etching treatment or the like, the substrate is required to be excellent in solvent resistance, alkali resistance, scratch resistance, and the like. However, the conventional surface treatment technology has not realized a substrate excellent in solvent resistance, alkali resistance, and scratch resistance.

  The present invention has been made in view of the above circumstances, and provides a composition for treating a substrate that can be used as a substrate excellent in solvent resistance, alkali resistance, and scratch resistance without impairing the appearance. The purpose is to do.

  As a result of intensive studies, the present inventors have found that the above problems can be solved by using a composition containing a specific component composition as a composition for substrate treatment, and have completed the present invention.

That is, the present invention is as follows.
[1]
(A) 80-95 parts by mass of one or more selected from the group consisting of tripentaerythritol octaacrylate , tripentaerythritol heptaacrylate , dipentaerythritol hexaacrylate,
(B) 5 to 20 parts by mass of a secondary thiol compound having two or more thiol groups in the molecule;
For a total amount of 100 parts by mass of the component (A) and the component (B), (C) 0.5 to 20 parts by mass of a photopolymerization initiator,
With respect to 100 parts by mass of the total amount of component (A) and component (B), (D) 100 to 300 parts by mass of solvent,
A composition for treating a substrate , comprising:
The substrate material used for the substrate treatment composition is triacetyl cellulose (TAC), polycarbonate (PC), acrylic polymer, cycloolefin polymer (COP), cycloolefin copolymer (COC), polyamide (PA The composition for base-material processing which is 1 type, or 2 or more types chosen from the group which consists of .
[2]
A method for producing a laminated substrate including the following steps;
(1) The process of apply | coating the composition for base-material treatment as described in [1] to at least one part of any one surface of a base material,
(2) A step of forming a resin layer on the surface of the substrate by irradiating the composition for substrate treatment applied to the surface with ultraviolet rays after the step (1).
[3]
A method for producing a laminated substrate including the following steps in random order;
(A1) The process of apply | coating the composition for base-material treatment as described in [1] to at least one part of the 1st surface of a base material,
(A2) After the step (a1), the composition for substrate treatment applied to the first surface is irradiated with ultraviolet rays, and a first resin layer is formed on the first surface of the substrate. Forming a process,
(B1) A step of applying the substrate treatment composition according to claim 1 to at least a part of the second surface opposite to the first surface;
(B2) After the step (b1), the substrate treatment composition applied to the second surface is irradiated with ultraviolet rays, and a second resin layer is formed on the second surface of the substrate. Forming.
[4]
The method for producing a laminated substrate according to [2] or [3], wherein the solvent contained in the composition for treating a substrate has a property of dissolving or swelling a material constituting the substrate.
[5]
(3) The method for producing a laminated base material according to [2], further comprising a step of heating the base material treatment composition applied onto the surface of the base material after the step (1). .
[6]
(A3) after the step (a1), heating the composition for treating a substrate applied on the first surface of the substrate;
(B3) after the step (b1), heating the substrate treatment composition applied on the second surface of the substrate;
The method for producing a laminated base material according to [3], further comprising:
[7]
The base material includes any one selected from the group consisting of triacetyl cellulose, polycarbonate, acrylic polymer, cycloolefin copolymer, and cycloolefin polymer;
The solvent according to any one of [2] to [6], wherein the solvent includes any one selected from the group consisting of a ketone solvent, an ester solvent, a glycol solvent, and a hydrocarbon solvent. A method for producing a substrate.
[8]
A substrate;
Resin formed on the surface of the substrate by applying a composition for treating a substrate containing the following components to at least a part of one surface of the substrate and irradiating with ultraviolet rays Layers,
Having a laminated substrate;
The substrate treatment composition is
(A) 80-95 parts by mass of one or more selected from the group consisting of tripentaerythritol octaacrylate , tripentaerythritol heptaacrylate , dipentaerythritol hexaacrylate,
(B) 20-5 parts by mass of a secondary thiol compound having two or more thiol groups in the molecule;
For a total amount of 100 parts by mass of the component (A) and the component (B), (C) 0.5 to 20 parts by mass of a photopolymerization initiator,
With respect to 100 parts by mass of the total amount of component (A) and component (B), (D) 100 to 300 parts by mass of solvent,
Contain,
The material of the base material is one selected from the group consisting of triacetyl cellulose (TAC), polycarbonate (PC), acrylic polymer, cycloolefin polymer (COP), cycloolefin copolymer (COC), and polyamide (PA), or 2 or more types .
[9]
A substrate;
It is formed on the first surface of the substrate by applying a composition for treating a substrate containing the following components to at least a part of the first surface of the substrate and irradiating with ultraviolet rays. A first resin layer;
The substrate treatment composition is applied to at least a part of the second surface of the base material and irradiated with ultraviolet rays, thereby forming a second surface on the second surface of the base material. A resin layer;
Having a laminated substrate;
The substrate treatment composition is
(A) 80-95 parts by mass of one or more selected from the group consisting of tripentaerythritol octaacrylate , tripentaerythritol heptaacrylate , dipentaerythritol hexaacrylate,
(B) 20-5 parts by mass of a secondary thiol compound having two or more thiol groups in the molecule;
For a total amount of 100 parts by mass of the component (A) and the component (B), (C) 0.5 to 20 parts by mass of a photopolymerization initiator,
With respect to 100 parts by mass of the total amount of component (A) and component (B), (D) 100 to 300 parts by mass of solvent,
Contain,
The material of the base material is one selected from the group consisting of triacetyl cellulose (TAC), polycarbonate (PC), acrylic polymer, cycloolefin polymer (COP), cycloolefin copolymer (COC), and polyamide (PA), or 2 or more types .

  ADVANTAGE OF THE INVENTION According to this invention, the composition for base-material processing which can be used as a base material excellent in solvent resistance, alkali resistance, and abrasion resistance without impairing an external appearance can be provided.

The conceptual diagram for demonstrating the solvent resistance test done in the Example is represented.

  Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be implemented with appropriate modifications within the scope of the gist thereof.

<Substrate treatment composition>
The composition for substrate treatment of this embodiment is
(A) 80 to 95 parts by mass of a compound having 4 or more (meth) acryloyl groups in the molecule;
(B) 5 to 20 parts by mass of a compound having two or more thiol groups in the molecule;
For a total amount of 100 parts by mass of the component (A) and the component (B), (C) 0.5 to 20 parts by mass of a photopolymerization initiator,
With respect to 100 parts by mass of the total amount of component (A) and component (B), (D) 100 to 300 parts by mass of solvent,
It is the composition for base-material processing containing this.

  By performing the surface treatment of the substrate using the substrate treatment composition of the present embodiment, a laminated substrate in which a resin layer is formed on the substrate can be obtained. Although details of the treatment method will be described later, a substrate (laminated substrate) excellent in solvent resistance, alkali resistance, and scratch resistance can be obtained by performing such surface treatment without impairing the appearance.

  Further, by using the substrate processing composition of the present embodiment, (i) the etching resistance of the substrate is greatly improved, and (ii) the substrate is thin even when the substrate is thin. Exhibit excellent etching resistance even at the end (side surface, cut surface, etc.), and (iii) be able to suppress warpage (curl) of the treated substrate even when the substrate is thin. , Etc. can also be expected.

  The reason why the above effect is obtained by using the substrate treating composition of the present embodiment is not certain, but is presumed as follows. First, since the composition for base material treatment includes not only the components (A) to (C) but also the component (D) at a specific ratio, not only the surface of the base material but also the inside of the base material is used for base material processing. The composition penetrates. Therefore, the curing reaction by the component (A), the component (B) and the component (C) proceeds not only on the surface of the substrate but also in the internal region. As a result, the solvent resistance, alkali resistance, and scratch resistance are improved not only on the coated surface but also on the cross-section (edge) surface when the substrate is cut to a predetermined size. Thereby, the tolerance with respect to the etching liquid etc. which are used for the etching process of an optical material or an electronic material improves (however, the effect | action of this embodiment is not limited to this).

<Base material>
An example of the substrate that can be used for the substrate treating composition of the present embodiment will be described.
The material for the substrate is not particularly limited as long as it is a material capable of forming a resin layer (described later) with the composition for substrate treatment. Specific examples of the base material include triacetyl cellulose (TAC), polycarbonate (PC), acrylic polymer, cycloolefin polymer (COP), cycloolefin copolymer (COC), polyamide (PA), and the like. . Among these, triacetyl cellulose, polycarbonate, acrylic polymer, cycloolefin copolymer, and cycloolefin polymer are preferable.

  As the triacetyl cellulose, a known one can be used. Triacetyl cellulose can be obtained, for example, by reacting cellulose with acetic anhydride and acetylating the hydroxyl group contained in the cellulose. Triacetyl cellulose may have a polar group introduced therein.

  Although the weight average molecular weight of a triacetyl cellulose is not specifically limited, It is preferable that it is 150,000-250,000, and it is more preferable that it is 180,000-220,000. The weight average molecular weight can be measured by gel permeation chromatography (GPC; solvent tetrahydrofuran).

  As the polycarbonate, any polymer including a monomer having a carbonate bond may be used, and a known one may be used. Although the ratio of the monomer which has a polycarbonate bond in a polycarbonate is not specifically limited, Preferably it is 50 mass% or more, More preferably, it is 60 mass% or more, More preferably, it is 70 mass% or more. As the polycarbonate, either a linear polycarbonate or a branched polycarbonate may be used.

  The weight average molecular weight of the polycarbonate is not particularly limited, but is preferably 10,000 to 200,000, and more preferably 20,000 to 120,000. The weight average molecular weight can be measured by gel permeation chromatography (GPC; solvent tetrahydrofuran).

  Examples of the acrylic polymer include a polymer having (meth) acrylic acid or an ester thereof as at least a monomer (hereinafter, these may be collectively referred to as “acrylic monomer”). In addition, (meth) acrylic acid means acrylic acid and / or methacrylic acid. The ratio of the acrylic monomer in the acrylic polymer is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, and still more preferably 100% by mass. .

  Specific examples of the acrylic polymer include, for example, methyl poly (meth) acrylate, methyl (meth) acrylate- (meth) acrylic acid copolymer, methyl (meth) acrylate- (meth) acrylic acid alkyl ester copolymer, ( And a (meth) acrylic acid-styrene copolymer.

  The weight average molecular weight of the acrylic polymer is not particularly limited, but is preferably 5,000 to 300,000, and more preferably 20,000 to 200,000. The weight average molecular weight can be measured by gel permeation chromatography (GPC; solvent tetrahydrofuran).

  The cycloolefin polymer can be obtained, for example, by a ring-opening polymerization reaction of cycloolefins (such as norbornene and derivatives thereof). The cycloolefin polymer may have a polar group introduced therein.

  The cycloolefin copolymer can be obtained, for example, by addition polymerization of cycloolefins (such as norbornene and derivatives thereof) and α-olefins (such as ethylene). The cycloolefin copolymer may have a polar group introduced therein.

  Polyamide can be obtained, for example, by co-condensation polymerization of diamines and dicarboxylic acids. The diamine may be either an aliphatic diamine or an aromatic diamine, but is preferably an aromatic diamine. The dicarboxylic acids may be aliphatic dicarboxylic acids or aromatic dicarboxylic acids, but are preferably aromatic dicarboxylic acids. Furthermore, a combination of aromatic diamines and aromatic carboxylic acids is more preferable.

  As a base material, the polymer mentioned above may be used individually by 1 type, and may use 2 or more types together.

  As the substrate, a film obtained by extruding the above-described polymer or the like (sometimes referred to as “sheet”) or the like can be used. The base material may be uniaxially stretched or biaxially stretched.

  The substrate may be a single layer or a multilayer of two or more layers. For example, a base material having a two-layer structure in which a polycarbonate and an acrylic polymer are coextruded.

  The thickness of the substrate is not particularly limited and can be appropriately selected depending on the intended use. As thickness of a base material, Preferably it is 5-200 micrometers, More preferably, it is 5-100 micrometers, More preferably, it is 5-80 micrometers. By setting the lower limit value of the thickness of the base material to the above value, it is possible to further prevent the base material from being cut during processing using the base material processing composition. By setting the upper limit value of the thickness of the base material to the above value, the composition for base material treatment can be sufficiently infiltrated into the base material during the surface treatment of the base material, and a further excellent effect can be obtained. Can be obtained.

<Ingredients>
Hereinafter, the components and the like of the composition for substrate treatment of the present embodiment will be described.

  The component (A) is a compound having 4 or more (meth) acryloyl groups in the molecule. The component (A) may be, for example, a monomer or an oligomer.

  Specific examples of the monomer (A) component include, for example, pentaerythritol polyethoxytetra (meth) acrylate, pentaerythritol polypropoxytetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, and ditrimethylolpropane tetra (meth). Examples include acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octaacrylate, and tripentaerythritol heptaacrylate.

  As the component (A) which is an oligomer, for example, epoxy (meth) acrylate, urethane (meth) acrylate, polyether urethane (meth) acrylate, polyester (meth) acrylate, silicone (meth) acrylate, polybutadiene (meth) acrylate, Examples of the polyamide (meth) acrylate include compounds having at least 4 acryloyl groups in the molecule. Among these, from the viewpoints of solvent resistance, crosslinking density, and yellowing, urethane (meth) acrylate is preferable, and urethane (meth) acrylate having 4 or more acryloyl groups is more preferable. A commercial item can also be used for these. Specific examples of commercially available products include, for example, “UA-306H”, “UA-306T”, “UA-306I” manufactured by Kyoeisha Chemical Co., Ltd .; “UV-1700B”, “UV-6300B” manufactured by Nippon Synthetic Chemical Co., Ltd. , “UV-7600B”, “UV-7605B”, “UV-7640B”, “UV-7650” B, etc .; Shin-Nakamura Chemical Co., Ltd., “U-4HA”, “U-6HA”, “UA-100H” ”,“ U-6LPA ”,“ U-15HA ”,“ UA-32P ”,“ U-324A ”; manufactured by Negami Kogyo Co., Ltd.,“ H-135 ”,“ UN-3220HA ”,“ UN-3220HB ”,“ UN-3220HC "," UN-3220HS ", etc. are mentioned.

  As the component (A), from the viewpoint of expressing sufficient solvent resistance after the substrate treatment composition has penetrated into the substrate, tripentaerythritol octaacrylate, tripentaerythritol heptaacrylate, dipentaerythritol hexaacrylate Etc. are preferred. These are more preferably those capable of realizing a high crosslinking density.

  (A) A component may be used individually by 1 type and may use 2 or more types together.

The component (B) is a compound having two or more thiol groups in the molecule.
Specific examples of the component (B) include, for example, 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, 1, 2-cyclohexanedithiol, decanedithiol, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, 1,4-butanediol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropio 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, pentaerythritol tetrakis (3-mercap) Butyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, dipentaerythritol hexathiopropionate, ester of polyhydric alcohol and mercaptopropionic acid, trimercaptopropionic acid tris (2-hydroxyethyl) Examples include isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, and 2- (N, N-dibutylamino) -4,6-dimercapto-s-triazine.

  As the component (B), secondary thiols are preferable from the viewpoint of solvent resistance and storage stability, and 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mer) More preferred are carbbutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, pentaerythritol tetrakis (3-mercaptobutyrate) and the like.

  (B) A component may be used individually by 1 type and may use 2 or more types together.

  (C) A component is a photoinitiator. The component (C) is not particularly limited as long as it is a radical-generating photopolymerization initiator. Specific examples of the component (C) include, for example, benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzylmethyl ketal, and alkyl ethers thereof; acetophenone, 2,2-dimethoxy-2-phenylacetophenone Acetophenones such as 1-hydroxycyclohexyl phenyl ketone; anthraquinones such as anthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone and 2-amylanthraquinone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal, and azo compounds Can be mentioned.

  The component (C) can be used in combination with a photopolymerization initiation auxiliary agent. Examples of such photopolymerization initiation assistant include tertiary amines such as triethanolamine and methyldiethanolamine; benzoic acid derivatives such as 2-dimethylaminoethylbenzoic acid and ethyl 4-dimethylaminobenzoate. .

  (C) A component may be used individually by 1 type and may use 2 or more types together.

  (D) A component is a solvent. By using a predetermined amount of solvent, the components contained in the composition for treating a substrate can be permeated into the inside of the substrate. The component (D) is not particularly limited as long as it dissolves at least the component contained in the composition for substrate treatment.

  Specific examples of the component (D) include ketone solvents, ester solvents, glycol solvents, hydrocarbon solvents, ether solvents, amide solvents, and the like. Among these, ketone solvents, ester solvents, glycol solvents, and hydrocarbon solvents are preferable from the viewpoint of easy penetration into the substrate.

  Examples of the ketone solvent include acetone, methyl ethyl ketone, diethyl ketone, dipropyl ketone, diisobutyl ketone, methyl isobutyl ketone (MIBK), cyclopentanone, cyclohexanone, methylcyclohexanone, methylcyclohexanone, and the like.

  Examples of the ester solvent include ethyl formate, propyl formate, n-pentyl formate, methyl acetate, ethyl acetate, methyl propionate, propion brew ethyl, n-pentyl acetate, Y-ptyrolactone, dimethyl carbonate and the like.

  Examples of the glycol solvent include methyl cellosolve, cellosolve, butyl cellosolve, cellosolve acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and the like.

  Examples of the hydrocarbon solvent include an aromatic hydrocarbon solvent and an aliphatic hydrocarbon solvent. Examples of the aromatic hydrocarbon solvent include toluene, xylene, cyclohexylbenzene, and the like. Examples of the aliphatic hydrocarbon solvent include n-hexane, n-heptane, cyclohexane and the like.

  Examples of the ether solvent include dibutyl ether, dimethoxymethane, dimethoxyethane, diethoxyethane, propylene oxide, dioxane, dioxolane, trioxane, tetrahydrofuran, anisole, phenetole and the like.

  Examples of the amide solvent include N-methyl-2-pyrrolidone and the like.

  (D) It is preferable that a component has a property which melt | dissolves or swells the material which comprises the base material mentioned later. Thereby, the component contained in the composition for base material treatment can be further permeated into the inside of the base material, and the obtained effect becomes more remarkable.

  Here, the property of dissolving the material constituting the substrate does not necessarily require the material to be completely dissolved. In addition, the property of swelling the material constituting the substrate refers to the property of increasing the volume of the material when the material is immersed in a solvent.

  From the above viewpoint, a suitable solvent can be selected according to the material constituting the substrate. For example, the base material includes any one selected from the group consisting of triacetyl cellulose, polycarbonate, acrylic polymer, cycloolefin copolymer, and cycloolefin polymer, and the solvent includes a ketone solvent, an ester solvent, and a glycol solvent. A combination containing any one selected from the group consisting of a solvent and a hydrocarbon solvent is preferable. Specific examples of more preferable combinations of the base material and the solvent include the following combinations.

  In the case of a substrate of triacetyl cellulose (TAC), at least one solvent selected from the group consisting of ether solvents, ketone solvents, ester solvents, glycol solvents, and amide solvents can be used. These solvents may be used alone or in combination of two or more.

  In the case of a polycarbonate or acrylic polymer substrate, at least one solvent selected from the group consisting of ether solvents, ketone solvents, ester solvents, glycol solvents, aromatic hydrocarbon solvents, and amide solvents is mentioned. It is done. These solvents may be used alone or in combination of two or more.

  In the case of a substrate of a cycloolefin polymer or a cycloolefin copolymer, at least one solvent selected from the group consisting of an aromatic hydrocarbon solvent and an aliphatic hydrocarbon solvent can be mentioned. These solvents may be used alone or in combination of two or more.

  In the case of a polyamide base material, at least one solvent selected from the group consisting of amide solvents, aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, and ketone solvents can be used. These solvents may be used alone or in combination of two or more.

  The content of the component (A) and the component (B) in the total amount of the component (A) and the component (B) of 100 parts by mass is not particularly limited, but the component (A) is 80 to 95 parts by mass, ) The component is preferably 20 to 5 parts by mass. When the content of the component (A) is 80 parts by mass or more, excellent coating strength can be imparted. When the content of the component (A) is 95 parts by mass or less, excellent solvent resistance can be imparted.

  Content of (C) component with respect to 100 mass parts of total amounts of (A) component and (B) component is 0.5-20 mass parts. When the content of the component (C) is less than 0.5 parts by mass, the solvent resistance and scratch resistance become insufficient. When the content of the component (C) exceeds 20 parts by mass, poor appearance due to yellowing or the like, and light resistance are insufficient. The content of (C) with respect to 100 parts by mass of the total amount of component (A) and component (B) is preferably 1 to 15 parts by mass, more preferably 2 to 10 parts by mass.

  Content of (D) component with respect to 100 mass parts of total amounts of (A) component and (B) component is 100-300 mass parts. When the content of component (D) is less than 100 parts by mass, the permeability to the substrate and the solvent resistance are insufficient. When the content of the component (D) exceeds 300 parts by mass, appearance defects due to whitening or deformation such as warpage may occur. The content of (D) with respect to 100 parts by mass of the total amount of component (A) and component (B) is preferably 130 to 270 parts by mass, more preferably 150 to 250 parts by mass.

  The composition for substrate processing of this embodiment may further contain other components other than the components described above. Such other components include, for example, trifunctional or lower compounds (monomers, oligomers, etc.) other than the components (A) and (B), inorganic fillers, dispersants, surfactants, reactive diluents, shakers, etc. Examples include modifiers, antifoaming agents, leveling agents, polymerization inhibitors, antifouling agents, and antistatic agents.

  The trifunctional or lower compound other than the component (A) and the component (B) may be a monomer or an oligomer. Specific examples thereof include 1,6-hexanediol diacrylate, dipropylene glycol diacrylate, tricyclodecane dimethanol diacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, and the like. When using such other compounds, it is preferable to appropriately adjust the content of the component (C) described above. As a result, it is possible to further reduce the curing shrinkage when the substrate treatment composition is cured.

<Method for producing laminated substrate>
According to this embodiment, a laminated base material can be manufactured using the composition for base material processing described above. As a method for producing such a laminated substrate, a method for producing a laminated substrate including the following steps is suitable.
(1): The process of apply | coating the composition for base-material treatment to at least one part of any one surface of a base material.
(2): The process of forming a resin layer on the surface of a base material by irradiating the composition for base material processing applied to the surface with ultraviolet rays after the step (1).

(1) The process will be described.
It does not specifically limit as a method of apply | coating the composition for base-material treatment to any one surface of a base material, A well-known method can be used. For example, a dipping method, a flow coating method, a spray method, a spin coating method, a barcode method, and the like can be given. Moreover, it can apply | coat using coating tools, such as a gravure coat, a roll coat, a blade coat, a comma coat, and an air knife coat.

  The coating amount of the substrate treatment composition is not particularly limited, but the thickness of the resin layer formed after coating is preferably 0.2 to 10 μm, more preferably 0.5 to 5 μm, still more preferably 0.00. It apply | coats so that it may become 5-3 micrometers. By setting the lower limit of the thickness of the resin layer to the above value, the solvent resistance, alkali resistance, and scratch resistance are further improved. By setting the upper limit of the thickness of the resin layer to the above value, appearance defects such as whitening due to a solvent or the like can be more effectively suppressed.

(2) The process will be described.
The resin layer is formed by irradiating the composition for substrate treatment applied to the surface of the substrate with ultraviolet rays. The irradiation condition and irradiation method of ultraviolet rays are not particularly limited, and suitable conditions can be adopted as appropriate.

The integrated quantity of ultraviolet light is not particularly limited, preferably 100~2,000mJ / cm ^2, more preferably 150~1,500mJ / cm ^2, more preferably 200~1,000mJ / cm ² It is. By setting the cumulative amount of ultraviolet light within the above range, the composition for treating a substrate can be efficiently cured, and the resin layer can be further adhered to the surface of the substrate.

  In this embodiment, it is preferable to further include a step of heating the composition for substrate treatment applied on the surface of the substrate after the steps (3) and (1). Thereby, (D) component can be volatilized efficiently. As a result, the resin layer can be further adhered to the surface of the substrate, and a further excellent effect can be obtained. Furthermore, when using a thermosetting initiator etc. as an initiator, not only volatilization of (D) component but thermosetting of the composition for base treatment can be anticipated. Examples of such a thermosetting initiator include azobisisobutyronitrile.

  (3) The process will be described. The step (3) may be at least after step (1). Therefore, (3) process may be performed before (2) process, (3) process may be performed after (2) process, and (3) process is performed simultaneously with (2) process. Also good.

  Examples of the heating method include hot air drying and far-infrared drying, but are not particularly limited. Although it does not specifically limit as heating temperature, Preferably it is 50-130 degreeC, More preferably, it is 60-120 degreeC, More preferably, it is 60-110 degreeC. Although it does not specifically limit as heating time, Preferably it is 50 to 300 second, More preferably, it is 60 to 240 second, More preferably, it is 60 to 180 second.

  Note that the heating is preferably performed in multiple stages by changing the heating temperature. In that case, you may change not only heating temperature but heating time as needed. Thereby, the effect acquired is further improved. For example, heating is performed at 60 to 80 ° C. for 20 to 40 seconds (first stage heating), and heating is performed at the first stage heating temperature + (20 to 40) ° C. for 50 to 70 seconds (second stage heating). It is preferable to perform heating (third stage heating) at a temperature of the second stage heating temperature + (20 to 40) ° C. for 20 to 40 seconds.

In the present embodiment, the resin layer may be provided only on one surface of the base material, or the resin layer may be provided on both surfaces of the base material. When providing a resin layer on both surfaces of a base material, the manufacturing method of a laminated base material including the following process is suitable.
(A1): The process of apply | coating the composition for base-material treatment to at least one part of the 1st surface of a base material.
(A2): After the step (a1), the step of irradiating the composition for base material treatment applied to the first surface with ultraviolet rays to form the first resin layer on the first surface of the base material .
(B1): A step of applying the substrate processing composition to at least a part of the second surface opposite to the first surface.
(B2): After the step (b1), the step of irradiating the composition for base material treatment applied to the second surface with ultraviolet rays to form the second resin layer on the second surface of the base material .

  By performing the steps (a1), (a2), (b1), and (b2), resin layers can be provided on both surfaces of the substrate. About the (a1) process and the (b1) process, the conditions of the (1) process mentioned above are employable. About the (a2) process and the (b2) process, the conditions of the (2) process mentioned above are employable.

  About the order of (a1) process, (a2) process, (b1) process, (b2) process, (a2) process is performed at least after (a1) process, and (b2) process is performed after (b1) process. What is necessary is just a thing, and the order between other each process is not specifically limited. For example, (a1) step, (a2) step, (b1) step, (b2) step is performed in this order; (a1) step, (b1) step, (a2) step, (b2) step is performed; For example, the steps (a1) and (b1) are performed simultaneously, and then the steps (a2) and (b2) are performed simultaneously.

In this embodiment, it is preferable to further include the following steps.
(A3): a step of heating the composition for substrate treatment applied on the first surface of the substrate after the step (a1),
(B3): A step of heating the substrate processing composition applied on the second surface of the substrate after the step (b1).

  By performing the steps (a3) and (b3), the resin layer can be more firmly formed on the first surface and the second surface. As the heating method and heating conditions that can be employed in the steps (a3) and (b3), the conditions of the above-described step (3) can be employed.

The order of the steps (a3) and (b3) may be any as long as the step (a3) is performed after the step (a1) and the step (b3) is performed after the step (b1). The order between each process is not specifically limited.
For example, in the steps (a1) to (a3), the steps (a1), (a2), and (a3) may be performed in this order, or the steps (a1), (a3), and (a2). You may do in order. Similarly, in the steps (b1) to (b3), the steps (b1), (b2), and (b3) may be performed in this order, or the steps (b1), (b3), and (b2). You may carry out in order of a process.
In the steps (a1) to (a3) and (b1) to (b3), the steps (b1) to (b3) may be performed after the steps (a1) to (a3) are performed. After performing the step (a1) and the step (b1), the step (a2), the step (a3), the step (b2), and the step (b3) may be performed.

<Laminated substrate>
As a laminated base material in which a resin layer is formed on any one surface of the base material, for example, the above-described base material treatment composition is applied to at least a part of the base material and any one surface of the base material. The laminated base material which has the resin layer formed on the surface of the base material by apply | coating and irradiating an ultraviolet-ray is mentioned.

  Examples of the laminated base material in which the resin layer is formed on both surfaces (first surface and second surface) of the base material include, for example, the base material and at least a part of the first surface of the base material. The base resin composition is applied and irradiated with ultraviolet rays to form at least a part of the first resin layer formed on the first surface of the base material and the second surface of the base material. The laminated base material which has the 2nd resin layer formed on the 2nd surface of a base material by apply | coating the composition for base-material processing and irradiating an ultraviolet-ray is mentioned.

  The laminated base material of this embodiment may further have another layer on the surface of the resin layer. Examples of the other layers include an antireflection layer for preventing light reflection, an adhesive layer for attaching a laminated base material to an adherend, and a protective layer for protecting the base material.

  Examples of the antireflection layer include a siloxane-based film, a fluorine-based film, or an acrylic film, and preferably include a siloxane-based film, a fluorine-based film, or an acrylic film that contains a low refractive nanofiller. It is done. By further including such an antireflection layer, it is possible to eliminate reflections or the like caused by reflection or incidence of light from the outside such as sunlight or fluorescent lamps.

  Examples of the adhesive layer include an adhesive layer using an acrylic adhesive, a urethane adhesive, a silicone adhesive, and the like. Moreover, you may further provide a peeling sheet on the adhesion layer as needed.

  Examples of the protective layer include various layers having scratch resistance and high hardness. By providing such a protective layer, the scratch resistance and hardness can be further improved.

  The laminated base material of this embodiment can be used for a flexible printed circuit board, a transparent conductive film, an electromagnetic wave shielding film, etc., for example. These can be suitably used as materials for various displays such as a plasma display (PDP) and a liquid crystal display (LCD), various icon sheets, and a touch panel sheet.

  The present invention will be described in more detail with reference to the following examples and comparative examples, but the present invention is not limited to the following examples.

<Base materials, etc.>
・ TAC film:
Comic Minolta Advanced Layer, “4UA” (film thickness 40 μm)
・ PC film:
"Pure Ace" manufactured by Teijin Chemicals Ltd. (film thickness 100μm)
Acrylic film An acrylic polymer was prepared by the following procedure, and an acrylic film (film thickness: 15 μm) was prepared using the polymer.
(1) Production of acrylic polymer In a reactor equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a reflux condenser, 60 parts by mass of ethyl acetate and 10 parts by mass of propylene glycol monobutyl ether were placed. Then, 68.5 parts by mass of methyl methacrylate, 14 parts by mass of butyl acrylate, 15 parts by mass of 2-hydroxyethyl methacrylate, and 2.5 parts by mass of acrylic acid were added to prepare a monomer mixture. After adding 25 parts by mass of this monomer mixture to the reactor and replacing the inside of the reactor with nitrogen gas, 1 part by mass of azobisisobutyronitrile was added as a polymerization initiator, and stirring was started. The reaction was heated to 80 ° C. and stirred for 10 minutes to carry out the initial reaction.
Then, 75 parts by mass of the remaining monomer mixture was added to the reactor over 2 hours. The mixture was further stirred for 1 hour while maintaining the temperature at reflux.
A solution prepared by dissolving 0.5 part by mass of azobisisobutyronitrile in 6 parts by mass of ethyl acetate was added dropwise over 30 minutes in a reflux state, and the reaction was further continued for 2 hours.
After completion of the reaction, 26 parts by mass of propylene glycol monobutyl ether and 134 parts by mass of toluene were added to the reaction product to obtain an acrylic polymer having a solid content of 30% by mass.
When the glass transition temperature of the acrylic polymer was measured using a differential scanning calorimeter (manufactured by Shimadzu Corporation, measuring device “DSC-60”, measuring condition: 3 ° C./min), it was 69.2 ° C. When the weight average molecular weight of the acrylic polymer was measured by gel permeation chromatography (manufactured by Tosoh Corporation, measuring device “HLC-8120 GPC”, measurement conditions: column temperature 40 ° C., flow rate 0.6 mL / min), 52 000.
(2) Production of acrylic film To 100 parts by mass (30 parts by mass of solid content) of the obtained acrylic polymer, a hexamethylene diisocyanate polyisocyanate compound (Asahi Kasei Chemicals, "E-405-70B") was added. The coating solution was prepared by sufficiently stirring. On a PET release film (“PET7511”, manufactured by Lintec Corporation), a coating solution is applied so that the thickness after drying is 15 μm, and using a hot air circulating dryer at 100 ° C. for 120 seconds. Dried. Thereafter, the film was cured for 10 days in an atmosphere of 40 ° C. to obtain an acrylic film (thickness: 15 μm).

<Ingredients>
Component (A): Mixture of tripentaerythritol octaacrylate and tripentaerythritol heptaacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., “Biscoat # 802”)
・ 10 functional urethane acrylate (10 functional; manufactured by Nippon Synthetic Chemical Industry Co., Ltd., “purple light UV1700-B”)
Component (B) Pentaerythritol tetrakis (3-mercaptobutyrate) (tetrafunctional; Showa Denko Co., Ltd., “Karenz MT PE1”)
・ 2-mercaptobenzoxazole (monofunctional; manufactured by Tokyo Chemical Industry Co., Ltd., “2-mercaptobenzoxazole”)
Component (C): Photopolymerization initiator 1-hydroxycyclohexyl phenyl ketone (BASF Japan, “Irgacure 184”)
Component (D): solvent, methyl isobutyl ketone (MIBK)
・ Cyclopentanone ・ Cyclohexanone

<Evaluation method>
The evaluation method of the produced laminated film is shown below.

(1) Appearance The surface of the laminated film was visually observed, and the appearance was evaluated based on the following criteria.
Good: No unevenness such as satin or whitening or yellowing was observed on the entire surface.
Defect: Unevenness such as satin, whitening or yellowing was confirmed on any of the surfaces.

(2) Solvent Resistance FIG. 1 is a conceptual diagram for explaining a solvent resistance test. First, the laminated film was cut into a size of 50 mm × 50 mm and immersed in methyl ethyl ketone (MEK) for 10 minutes.
After immersion, the laminated film was taken out and allowed to stand at room temperature for 60 minutes to volatilize the solvent. The distance (refer to L1 to L4 in FIG. 1) swelled before and after the immersion was measured for the four ends of the laminated film, and the arithmetic average ((L1 + L2 + L3 + L4) / 4) was defined as the swelling length L. Based on this swelling length, how much the laminated film swelled was evaluated. In addition, distance L1-L4 is the shortest distance of the edge part of the laminated | multilayer film before immersion, and the edge part of the laminated | multilayer film after immersion.
Good: The swelling length L of the laminated film was less than 3 mm.
Defect: The swelling length L of the laminated film was 3 mm or more.

(3) Alkali resistance First, the laminated film was cut into a size of 50 mm × 50 mm and immersed in a 5% aqueous sodium hydroxide solution for 10 minutes. After immersion, the laminated film was taken out and washed with pure water, and then allowed to stand at room temperature for 60 minutes to volatilize water. The appearance change of the laminated film before and after the test was visually confirmed.

(4) Scratch resistance First, the laminated film was cut into a size of 100 mm × 100 mm. Using # 0000 steel wool, a load of 100 g / cm ² was applied to the surface and rubbed 10 times at a speed of 300 mm / sec. Thereafter, the surface was wiped with a clean wipe, and the state was visually confirmed.

<Example 1>
Each component shown in Table 1 was put in a plastic container and stirred at 23 ° C. for 2 minutes to obtain a composition for substrate treatment. The composition for substrate processing was apply | coated to the surface of a TAC film using the micro gravure coater, and it dried on 70 degreeC for 30 second, 100 degreeC for 60 second, and 120 degreeC for 30 second conditions. And using the high pressure mercury lamp, the ultraviolet-ray was irradiated so that the integrated light quantity might be set to 400 mJ / cm < ² >, and the laminated film was obtained. Various physical properties of the obtained laminated film were evaluated. In addition, the obtained laminated | multilayer film did not have curvature (curl) etc., but was able to maintain the favorable shape as a film.

<Examples 2-6, Comparative Examples 1-6>
A laminated film was obtained in the same manner as in Example 1 except that a composition for substrate treatment was produced under the conditions described in Table 1 and a laminated film was produced using the composition. Various physical properties of the obtained laminated film were evaluated. In addition, all the laminated films of Examples 2-6 did not have warp (curl) or the like, and were able to maintain a good shape as a film.

  Tables 1 and 2 show the production conditions and evaluation results of each example and each comparative example.

  From the above, it was confirmed that at least each of the examples was excellent in appearance, solvent resistance, alkali resistance, and scratch resistance.

  The composition for substrate treatment according to the present invention and the laminated substrate obtained using the composition are as various displays such as a plasma display (PDP) and a liquid crystal display (LCD), various icon sheets, a sheet for a touch panel, etc. Can be used in a wide range of fields.

L1, L2, L3, L4 ... distance

Claims (9)

(A) 80-95 parts by mass of one or more selected from the group consisting of tripentaerythritol octaacrylate , tripentaerythritol heptaacrylate , dipentaerythritol hexaacrylate,
(B) 5 to 20 parts by mass of a secondary thiol compound having two or more thiol groups in the molecule;
For a total amount of 100 parts by mass of the component (A) and the component (B), (C) 0.5 to 20 parts by mass of a photopolymerization initiator,
With respect to 100 parts by mass of the total amount of component (A) and component (B), (D) 100 to 300 parts by mass of solvent,
A composition for treating a substrate , comprising:
The substrate material used for the substrate treatment composition is triacetyl cellulose (TAC), polycarbonate (PC), acrylic polymer, cycloolefin polymer (COP), cycloolefin copolymer (COC), polyamide (PA The composition for base-material processing which is 1 type, or 2 or more types chosen from the group which consists of . A method for producing a laminated substrate including the following steps;
(1) The process of apply | coating the composition for base-material treatment of Claim 1 to at least one part of any one surface of a base material,
(2) A step of forming a resin layer on the surface of the substrate by irradiating the composition for substrate treatment applied to the surface with ultraviolet rays after the step (1). A method for producing a laminated substrate including the following steps in random order;
(A1) The process of apply | coating the composition for base-material treatment of Claim 1 to at least one part of the 1st surface of a base material,
(A2) After the step (a1), the composition for substrate treatment applied to the first surface is irradiated with ultraviolet rays, and a first resin layer is formed on the first surface of the substrate. Forming a process,
(B1) A step of applying the substrate treatment composition according to claim 1 to at least a part of the second surface opposite to the first surface;
(B2) After the step (b1), the substrate treatment composition applied to the second surface is irradiated with ultraviolet rays, and a second resin layer is formed on the second surface of the substrate. Forming.   The method for producing a laminated substrate according to claim 2 or 3, wherein the solvent contained in the composition for treating a substrate has a property of dissolving or swelling a material constituting the substrate.   (3) The manufacturing method of the laminated base material of Claim 2 which further includes the process of heating the said composition for base-material processes apply | coated on the said surface of the said base material after the said (1) process. . (A3) after the step (a1), heating the composition for treating a substrate applied on the first surface of the substrate;
(B3) after the step (b1), heating the substrate treatment composition applied on the second surface of the substrate;
The manufacturing method of the laminated base material of Claim 3 which further contains these. The base material includes any one selected from the group consisting of triacetyl cellulose, polycarbonate, acrylic polymer, cycloolefin copolymer, and cycloolefin polymer;
The laminated base material according to any one of claims 2 to 6, wherein the solvent includes any one selected from the group consisting of a ketone solvent, an ester solvent, a glycol solvent, and a hydrocarbon solvent. Manufacturing method. A substrate;
Resin formed on the surface of the substrate by applying a composition for treating a substrate containing the following components to at least a part of one surface of the substrate and irradiating with ultraviolet rays Layers,
Having a laminated substrate;
The substrate treatment composition is
(A) 80-95 parts by mass of one or more selected from the group consisting of tripentaerythritol octaacrylate , tripentaerythritol heptaacrylate , dipentaerythritol hexaacrylate,
(B) 20-5 parts by mass of a secondary thiol compound having two or more thiol groups in the molecule;
For a total amount of 100 parts by mass of the component (A) and the component (B), (C) 0.5 to 20 parts by mass of a photopolymerization initiator,
With respect to 100 parts by mass of the total amount of component (A) and component (B), (D) 100 to 300 parts by mass of solvent,
Contain,
The material of the base material is one selected from the group consisting of triacetyl cellulose (TAC), polycarbonate (PC), acrylic polymer, cycloolefin polymer (COP), cycloolefin copolymer (COC), and polyamide (PA), or 2 or more types . A substrate;
It is formed on the first surface of the substrate by applying a composition for treating a substrate containing the following components to at least a part of the first surface of the substrate and irradiating with ultraviolet rays. A first resin layer;
The substrate treatment composition is applied to at least a part of the second surface of the base material and irradiated with ultraviolet rays, thereby forming a second surface on the second surface of the base material. A resin layer;
Having a laminated substrate;
The substrate treatment composition is
(A) 80-95 parts by mass of one or more selected from the group consisting of tripentaerythritol octaacrylate , tripentaerythritol heptaacrylate , dipentaerythritol hexaacrylate,
(B) 20-5 parts by mass of a secondary thiol compound having two or more thiol groups in the molecule;
For a total amount of 100 parts by mass of the component (A) and the component (B), (C) 0.5 to 20 parts by mass of a photopolymerization initiator,
With respect to 100 parts by mass of the total amount of component (A) and component (B), (D) 100 to 300 parts by mass of solvent,
Contain,
The material of the base material is one selected from the group consisting of triacetyl cellulose (TAC), polycarbonate (PC), acrylic polymer, cycloolefin polymer (COP), cycloolefin copolymer (COC), and polyamide (PA), or 2 or more types .