TWI733771B - Curable resin composition - Google Patents

Abstract

The present invention is characterized in that the curable composition that guarantees the adhesion between the inorganic substrate and the organic substrate at the same time contains (meth)acrylic oligomer (component A) and (meth)acrylic acid with a molecular weight of 5,000 or more Base monomer (component B), and at least one radical polymerization initiator (component C) selected from the group of photo-radical polymerization initiators and thermal radical polymerization initiators, and the viscosity is 150mPa˙s or less The curable resin composition.

Description

Curable resin composition

The present invention relates to a curable resin composition

It is known that inkjet printing using inkjet ink is a method that can form a desired pattern on a substrate at a lower cost and a very thin resin layer (film). This type of inkjet ink is a photocurable inkjet ink containing a monofunctional polymerizable monomer having a hydroxyl group, a difunctional (meth)acrylate, and a photopolymerization initiator, as proposed in Patent Document 1.

Recently, as display devices such as displays have become thinner, the bonding agent for display elements and components such as cover lenses including front panels, panels, and filters, and TFTs (thin film diodes) is proposed in Patent Document 2. It contains urethane (meth)acrylate oligomers with more than 2 (meth)acrylic groups in one molecule, and (meth)acrylates with hydroxyl groups, and non-radical polymerization It is an ultraviolet curable adhesive composition with a flexible component and a photo-radical polymerization initiator.

Prior art literature Patent literature

Patent Document 1: Japanese Patent Application Publication No. 2008-63556

Patent Document 2: JP 2014-118508 A

In recent years, a method of bonding components for image display devices has been developed, such as a thin coating and inkjet bonding method. Therefore, an adhesive corresponding to it is also required. However, the inkjet can be applied to a degree below 150mPa˙s, so the viscosity is extremely low. Therefore, the addition method disclosed in the examples of Patent Document 2 is difficult to guarantee both inorganic substrates such as glass and organic substrates such as thin films. The next force.

In order to solve the above-mentioned problems, the object of the present invention is to provide a light and thermosetting resin composition that can have excellent adhesion between the substrates even when the inorganic substrate and the organic substrate are bonded.

The present inventors discovered that it is characterized by a (meth)acrylic oligomer (component A) with a molecular weight of 5,000 or more, and a (meth)acrylic monomer (component B), which is initiated by radical polymerization with light and/or heat. (Component C) and a composition with a viscosity of 150 mPa˙s or less can solve the aforementioned problems and complete the present invention.

The present invention is constituted by the following.

[1] A curable resin composition containing a (meth)acrylic oligomer (component A) with a molecular weight of 5,000 or more, a (meth)acrylic monomer Body (component B), and at least one radical polymerization initiator (component C) selected from the group of photo-radical polymerization initiators and thermal radical polymerization initiators, and the viscosity is 150mPa˙s or less.

[2] The curable resin composition according to [1], wherein component B is a (meth)acrylic monomer containing 10 mPa˙s or less.

[3] The curable resin composition of [1] or [2], wherein component B is an alicyclic (meth)acrylic monomer, a hydroxyl-containing (meth)acrylic monomer, and C ₆ ~ C ₃₀ alkyl (meth)acrylic monomer.

[4] The curable resin composition according to any one of [1] to [3], wherein the component A is 30 parts by weight or less with respect to 100 parts by weight of the total of the component A and the component B.

[5] The curable resin composition according to any one of [1] to [4], which is an adhesive.

[6] The curable resin composition of any one of [1] to [4], which is used in spin coaters, die coaters, quantitative dispensers, inkjet coating, screen printing, and More than one method selected from a group of gravure printing houses.

According to the present invention, it is possible to provide a light and thermosetting resin composition that can have excellent adhesion between the substrates even when an inorganic substrate and an organic substrate are bonded.

[Definition of terms]

"(Meth)acrylate" means at least one of acrylate and methacrylate.

"(Meth)acryloyl group" means at least one of an acryloyl group and a methacryloyl group.

"(Meth)acryl group" means at least one of an acrylic group and a methacryl group.

[Curable resin composition]

The curable resin composition (hereinafter simply referred to as "composition") is a (meth)acrylic oligomer (component A) with a molecular weight of 5,000 or more, a (meth)acrylic monomer (component B), and At least one kind of radical polymerization initiator (component C) selected from the group of photo radical polymerization initiators and thermal radical polymerization initiators, and the viscosity is 150 mPa˙s or less.

((Meth)acrylic oligomer with molecular weight above 5,000 (component A))

The (meth)acrylic oligomer with a molecular weight of 5,000 or more (component A) has one or more (meth)acrylic groups in the molecule. The molecular weight of the (meth)acrylic oligomer is preferably 5,000 to 100,000, more preferably 10,000 to 70,000, particularly preferably 20,000 to 50,000. The molecular weight in this specification is the weight average molecular weight calculated by gel permeation chromatography (GPC) using the calibration curve of standard polystyrene.

The (meth)acrylate oligomer is not particularly limited, and for example, it is made of bone (Meth)acrylate oligomers with polyurethane frame, (meth)acrylate oligomers with polyisoprene frame, and (meth)acrylates with polybutadiene frame More than one selected from the group of oligomers. One or two or more of these (meth)acrylate oligomers can be used.

<(Meth)acrylate oligomer with polyurethane skeleton>

(Meth)acrylate oligomers with polyurethane in the skeleton, such as aliphatic series (except for rubber series and hydrogenated rubber series described later), polybutadiene and polyisoprene groups One or more rubber series selected from the group, one or more hydrogenated rubber series selected from the group of hydrogenated polybutadiene and hydrogenated polyisoprene, polyether series, polycarbonate series, polyester It is a urethane (meth)acrylate oligomer or a combination of these. Commercially available products with polyurethane skeleton (component A) such as UV-3700B (manufactured by Nippon Gosei: molecular weight 38,000), (UA10000B (manufactured by KSM: molecular weight 25,000), UN7700 (manufactured by Negami Kogyo Co., Ltd.: molecular weight) 20,000), UN-9200A (Negami Industry Co., Ltd.: molecular weight 15,000), UN-9000H (Negami Industry Co., Ltd.: molecular weight 5,000), EB230 (Decher Co., Ltd.: molecular weight 5,000), etc.

The urethane (meth)acrylate can be obtained by reacting an organic diisocyanate with a hydroxyl group-containing (meth)acrylate compound like the method described in JP 2008-260898 A, for example.

<<Organic Diisocyanate>>

The organic diisocyanate can be one with more than 2 isocyanato groups The compound is not particularly limited, and can be aromatic, aliphatic or alicyclic polyisocyanate, such as tolyl diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified High quality diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, tetramethylmethylene diisocyanate, isophores Polyisocyanates such as ketone diisocyanate, norbornene diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, phenylene diisocyanate, lysine triisocyanate, naphthalene diisocyanate, etc., or such Polyisocyanate and polyol are reacted with urethane prepolymers containing isocyanate groups at the end, etc.

<<(meth)acrylate compound containing hydroxyl group>>

The (meth)acrylate compound containing a hydroxyl group may be a (meth)acrylate compound having one or more hydroxyl groups in the molecule, and is not particularly limited. Specific examples of such hydroxyl-containing (meth)acrylate compounds include those described later in component B, such as 2-hydroxyethyl (meth)acrylic acid phosphate, etc., which contain phosphorus atoms and have one or more in the molecule The hydroxyl (meth)acrylate compound, and glycerol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, etc., which have 2 or more hydroxyl groups in the molecule (Meth)acrylate compound.

<(Meth)acrylate oligomer with polyisoprene in its skeleton and (meth)acrylate oligomer with polybutadiene in its skeleton>

The (meth)acrylate oligomer with polyisoprene in its skeleton and the (meth)acrylate oligomer with polybutadiene in its skeleton may be hydrogen additives. Commercially available (meth)acrylate oligomers having polybutadiene in the skeleton and (meth)acrylate oligomers having polyisoprene in the skeleton can be used. For example, commercially available products of (meth)acrylate oligomers having polyisoprene in the skeleton, such as UC-1 (manufactured by Curaray Corporation: molecular weight 25,000), UC-203 (manufactured by Curaray Corporation: molecular weight 35,000) Wait. In this specification, the (meth)acrylate oligomer with polyisoprene in the skeleton and the (meth)acrylate with polybutadiene in the skeleton are those that do not have a urethane bond.

The (meth)acrylate oligomer is preferably a (meth)acrylate oligomer having polyurethane in the skeleton, more preferably a polyether-based urethane (meth)acrylate Oligomers, polyester-based urethane (meth)acrylate oligomers, aliphatic-based urethane (meth)acrylate oligomers, rubber-based urethane (meth)acrylate oligomers, rubber-based urethane (meth) ) One or more selected from the group of acrylate oligomers and hydrogenated rubber-based urethane (meth)acrylate oligomers. The (meth)acrylate oligomer may be used alone or in combination of two or more.

((Meth)acrylic monomer (component B))

The (meth)acrylic monomer (component B) may be a monomer resin having one or more (meth)acrylic groups in the molecule, and is not particularly limited, but is preferably composed of monofunctional (meth)acrylate monomers. More than one selected from the group of bodies. The viscosity of component B is not particularly limited, but is preferably 10 mPa˙s or less, and more preferably 8 mPa˙s or less. When component B has this kind of viscosity, it tends to decrease the efficiency Low composition viscosity.

<Monofunctional (meth)acrylate monomer>

The monofunctional (meth)acrylate monomer may be a (meth)acrylate compound having one (meth)acrylic acid group in the molecule, and is not particularly limited. For example, it may be alicyclic (meth)acrylate or containing One or more selected from the group of hydroxyl (meth)acrylate, alkyl (meth)acrylate, and aromatic (meth)acrylate.

The alkyl (meth)acrylate is not particularly limited, for example, n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethyl Hexyl (meth)acrylate, isooctyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl (Meth)acrylate and the like. The alkyl (meth)acrylate is preferably a C ₆ to C ₃₀ alkyl (meth)acrylic monomer. Alkyl (meth)acrylate can impart softness to the hardened product, and reduce the viscosity of the composition more efficiently, and reduce the odor of the composition. The alkyl (methyl) group _{of C 6} ~ C _{30 is preferred.} Acrylate, the C ₆ ~ C ₃₀ alkyl group can be linear or branched, and the viewpoint that better adhesion can be obtained is branched. The carbon number of the C ₆ -C ₃₀ alkyl group is preferably 6-20, more preferably 8-16.

Hydroxy-containing (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxyl Hydroxy-substituted alkyl (meth)acrylates such as butyl (meth)acrylate, and 2-(meth)acryloyloxyethyl-2- Hydroxypropyl phthalate, 2-hydroxy-3-(meth)acryloxypropyl (meth)acrylate, caprolactone modified 2-hydroxyethyl (meth)acrylate, cyclohexane Hydroxyl-containing (meth)acrylates other than alkyl (meth)acrylates other than hydroxy-substituted alkyl (meth)acrylates such as dimethanol mono(meth)acrylates, etc.

Alicyclic (meth)acrylates such as dicyclopentenyloxyethyl (meth)acrylate, norbornene (meth)acrylate, dicyclopentyl (meth)acrylate, isobornyl Base (meth)acrylate and the like.

Component B has better adhesion to both inorganic substrates and organic substrates. It is more preferable to contain alicyclic (meth)acrylate, hydroxyl-containing (meth)acrylate, and C ₆ ~C ₃₀ The alkyl (meth) acrylate.

(At least one radical polymerization initiator selected from the group of photo radical polymerization initiators and thermal radical polymerization initiators (component C))

In order to promote hardening, the composition may contain at least one radical polymerization initiator selected from the group of photo radical polymerization initiators and thermal radical polymerization initiators. The radical polymerization initiator may be used alone or in combination of two or more kinds. When the composition contains a photoradical polymerization initiator, the composition is a photocurable resin composition that is cured by energy rays. When the composition contains a thermal radical polymerization initiator, the composition is a thermosetting resin composition that is cured by heat. When the composition contains a photo radical polymerization initiator and a thermal radical polymerization initiator, the composition is a light and/or thermosetting resin composition that is cured by energy rays and/or heat.

<Photo-radical polymerization initiator>

The photoradical polymerization initiator may be a compound that generates radicals by light irradiation, and is not particularly limited. Optical radical polymerization initiators such as benzophenone, diacetyl ester, benzyl ester, benzidine, ω-bromoacetone benzene, chloroacetone, acetophenone, 2,2-diethoxy acetone benzene , 2,2-Dimethoxy-2-phenylacetone, p-dimethylamino acetonitrile; p-dimethylaminopropiophenone, 2-chlorobenzophenone, p,p'- Bisdiethylamino benzophenone, Michler's ketone, benzyl methyl ether, benzyl isobutyl ether, benzyl-n-butyl ether, benzyl dimethyl ketal, 1- Hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-ketone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, methyl phenyl ketone Carbonyl-based photopolymerization initiators such as formate, 2,2-diethoxyacetbenzene and 4-N,N'-dimethylacetonitrile; diphenyl disulfide and dibenzyl disulfide Sulfide-based photopolymerization initiators such as sulfides; Quinone-based photopolymerization initiators such as benzoquinone and anthraquinone; Azo-based photopolymerization initiators such as azobisisobutyronitrile and 2,2'-azobispropane UV light initiators such as reagents, and 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butane-1-one, 2-dimethylamino-2 -(4-Methyl-benzyl)-1-(4-morpholinylphenyl)-butan-1-one, bis(2,4,6-trimethylphenanyl)-phenylphosphine oxidation It can be a visible light initiator such as 2,4,6-trimethylphenanyl-diphenylphosphine oxide.

From the viewpoint of increasing the curing speed and reducing coloration after photocuring, the photoradical polymerization initiator is preferably a carbonyl-based photopolymerization initiator, and particularly preferably 1-hydroxy-cyclohexyl-phenyl-ketone.

The photoradical polymerization initiator may be used alone or in combination of two or more kinds.

<Thermal radical polymerization initiator>

The thermal radical polymerization initiator may be a compound that generates free radicals by heat, and is not particularly limited. For example, organic peroxides and azo compounds, etc., are preferably organic peroxides.

The organic peroxide may be an organic compound containing a peroxy group (-OO-), such as diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, peroxy Esters, peroxycarbonates, etc.

Specific examples of organic peroxides include dilaurel peroxide, diphenyl peroxide, bis-3,5,5-trimethylhexyl peroxide, and diamino peroxides; 1. 1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide (e.g. Kayaku H manufactured by Aiguzhou Chemicals Co., Ltd.), t-butyl hydroperoxide-like hydrogen peroxide Oxides; t-hexylperoxy 2-ethylhexanoate, dipentyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, 1, 3-bis(t-butylperoxyisopropyl)benzene, t-butylpentyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis( t-butylperoxy) dialkyl peroxides like hexyne-3; 2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane, 1,1-di- Peroxyketals like t-butylperoxycyclohexane and 2,2-di-t-butylperoxybutane; 1,1,3,3-tetramethylbutylperoxyneodecanoic acid Esters, α-cumylperoxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxyneobutyrate, t-butylperoxytrimethyl acetate, 1, 1,3,3-Tetramethylbutylperoxy 2-ethylhexanoate, t-pentylperoxy 2-ethylhexanoate, t-butylperoxy 2-ethylhexanoate, two -t-butylperoxyhexahydroterephthalate, t-pentylperoxy 3,5,5-trimethylhexanoate, t-butylperoxyacetate, t-butylperoxy Peroxy esters like oxybenzoate, t-hexylperoxybenzoate, t-pentylperoxybenzoate Class; di-2-ethylhexylperoxydicarbonate, diisopropylperoxydicarbonate, t-butylperoxyisopropyl carbonate, t-butylperoxy2-ethylhexyl carbonate , 1,6-bis(t-butylperoxycarboxy) hexane-like peroxycarbonate, etc.

Azo compounds such as azobisisobutyronitrile, 2,2'-azobis(2-methylisobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), Dimethyl-2,2'-azobis(isobutyrate), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) and the like.

Commercially available thermal radical polymerization initiators can be used. From the viewpoint of stability and harmfulness, the thermal radical polymerization initiator is preferably an organic peroxide, and particularly preferably a peroxy ester. Furthermore, from the viewpoint of the balance between the stability of the composition and the curing temperature, the organic peroxide preferably has a one-hour half-life temperature of 50 to 110°C as an indicator of the inactivation of the organic peroxide.

The thermal radical polymerization initiator may be one type or two or more types used in combination.

(Other ingredients)

The composition may contain other components within a range that does not impair the effects of the present invention. Other ingredients such as plasticizers, coupling agents, polymerization inhibitors, adhering agents, antioxidants, defoamers, pigments, fillers, chain transfer agents; light stabilizers, surface tension modifiers, leveling agents; UV absorbers One or more selected from the group of anti-foaming agents and anti-foaming agents. For these, components known to those in the field of inkjet coating compositions can be used.

(Viscosity of composition)

The viscosity of the composition is below 150mPa˙s. Because it is such a low-viscosity composition, it can be coated on the substrate in a thinner film thickness. The viscosity of the composition is preferably 100 mPa˙s or less, particularly preferably 80 mPa˙s or less. The lower limit of the viscosity of the composition may be a value that can be ink-jet coated, and is not particularly limited, and may be less than the viscosity measured by a viscometer. Although the lower limit of the viscosity of the composition is not limited, the viscosity of the composition can be, for example, 1 mPa˙s or more. Viscosity is the value measured with a cone plate viscometer at 25°C under atmospheric pressure.

(Preferred composition)

The content of Component A in the composition is preferably 30 parts by weight or less with respect to 100 parts by weight of the total of Component A and Component B, more preferably 20 parts by weight or less, and particularly preferably 10 parts by weight or less. When the content of component A is in the aforementioned range, it tends to effectively reduce the viscosity of the composition and have better adhesion.

The content of the photo-radical polymerization initiator in the composition is preferably 0.1-20 parts by weight, preferably 0.5-15 parts by weight, more preferably 0.5-10 parts by weight relative to 100 parts by weight of the total of component A and component B . When the content of the photoradical polymerization initiator is in the aforementioned range, the composition can be cured efficiently by irradiating energy rays.

The content of the thermal radical polymerization initiator in the composition is preferably 0.01-15 parts by mass relative to 100 parts by weight of the total of component A and component B, preferably 0.1-10 parts by mass, more preferably 0.5-5 parts by mass . When the content of the thermal radical polymerization initiator is in the aforementioned range, the composition can be cured efficiently by heating.

The total content of the other components in the composition is preferably 0.01 to 15 parts by mass relative to 100 parts by weight of the total of component A and component B, preferably 0.1 to 10 parts by mass, and particularly preferably 1 to 5 parts by mass.

The curable component of the composition is preferably composed only of component A and component B. When the curable component is formed of only component A and component B, the composition will not contain other curable components other than component A and component B such as epoxy resin. The curable component at this time refers to a component that can be polymerized and crosslinked by irradiation with light and heating.

(Preparation method of composition)

The manufacturing method of the composition may be obtained by a manufacturing method including a step of mixing Component A, Component B, Component C, and other components added as appropriate. The mixing method is not particularly limited, and various metals, plastic containers, stirring blades, mixers, etc. can be used.

(How to harden the composition)

When the composition contains a photoradical polymerization initiator, the composition can be cured by energy rays. When the composition contains a thermal radical polymerization initiator, the composition can be hardened by heating. When the composition contains an optical radical polymerization initiator and a thermal radical polymerization initiator, the composition can be hardened by energy rays and/or heating.

<Hardened by energy rays>

The energy rays are not particularly limited, and active energy rays such as visible light, ultraviolet rays, X-rays, and electron rays can be used. The energy rays are preferably ultraviolet rays. UV The linear light source can be a light source capable of emitting ultraviolet (UV). Ultraviolet light sources such as metal halide lamps, high-pressure mercury lamps, xenon lamps, mercury xenon lamps, halogen lamps, pulsed xenon lamps, LEDs, etc.

The irradiation amount when irradiating the energy ray is preferably such that the cumulative light amount of the energy ray is 500 to 10,000 mJ/cm ² . The accumulated light amount is preferably 1,000 to 8,000 mJ/cm ² , and more preferably 1,000 to 6,000 mJ/cm ² .

<harden by heating>

The heating temperature and heating time can be the temperature and time that can heat the composition to bond the substrates to each other, and are not particularly limited. The heating temperature is preferably 70 to 120°C, more preferably 80 to 110°C. The heating time is preferably 10 minutes to 2 hours, more preferably 20 minutes to 100 minutes.

(Purpose of composition)

The composition can be used as a composition for forming a hardened product on a substrate and an adhesive for bonding the substrates to each other, and is preferably used as an adhesive. In addition, since the composition has a low viscosity, it can be coated on a substrate in a thin film thickness, so it can be used as a spin coater, die coater, metering dispenser, inkjet coating (inkjet printing), web The composition for more than one method selected from the group of plate printing and gravure printing is preferably used as a composition for inkjet coating. Furthermore, the composition is more preferably used as an adhesive for bonding substrates to each other by inkjet coating. Hereinafter, a method of manufacturing a laminate obtained by bonding the base materials to each other using the composition will be described.

<Manufacturing method of laminated body>

The manufacturing method of the laminate includes the following steps (A), (B), and (C).

(A) A step of forming a curable resin composition layer on the base material 1 using a curable resin composition, (B) a step of bonding the base material 2 to the cured resin layer to obtain a bonded body, and (C) The step of heating and/or irradiating the laminated body with energy rays to obtain a laminated body.

<Laminated body>

In the laminate, the base material 1 and the base material 2 are joined to each other with a cured product of a curable resin composition interposed therebetween. The substrate 1 and the substrate 2 are, for example, substrates formed of an inorganic substrate, an organic substrate, or a mixture of inorganic and organic. Inorganic substrates, for example, one or more selected from the group of glass, metal and ceramics. Organic substrates such as plastics. The substrate 1 and the substrate 2 may be the same substrate or different substrates. In addition to the substrate 1 and the substrate 2, the laminate may further contain other substrates, and the bonding method of the substrates is not particularly limited.

The substrate 1 and the substrate 2 may be light-transmitting members or non-light-transmitting members. The light-transmitting member may have light-transmitting properties corresponding to the purpose of the laminated body. For example, when the laminated body is an image display device, it may have visible light-transmitting properties to the extent that the image formed by the display body can be distinguished. Translucent members such as glass, (meth)acrylic resin, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyimide, polyester, cyclic olefin polymerization Plate or sheet materials such as objects. These can be implemented hard on one or both sides Coding processing, anti-reflection processing, anti-glare processing, anti-fouling processing, anti-fog processing, polarization processing, wavelength cutting processing, etc. In addition, a light-shielding layer can be formed on the light-transmitting member. Such light-transmitting components include image sheets and decorative panels.

The opaque member can be an opaque organic material, an opaque inorganic material, or a combination of these, and is not particularly limited. Light-impermeable components such as ceramic plate or sheet materials such as alumina, stainless steel and other metal sheets after insulation treatment such as surface oxidation, plate materials or sheet materials of thermosetting resins, and thermoplastic resins. Specific examples of such opaque components include liquid crystal display panels, organic EL display panels, protective panels, touch panels, organic EL elements, filters, and other formed components.

For example, by using one of the substrate 1 or the substrate 2 as a display body and the other as a translucent member or an opaque member, laminates of various image display devices can be manufactured. The specific aspect is as follows.

(1) A liquid crystal display device can be manufactured by making one of the substrate 1 or the substrate 2 a liquid crystal display panel and the other a light-transmitting member.

(2) A so-called top emission type organic EL display device can be manufactured by making one of the base material 1 or the base material 2 an organic EL display panel, and the other as a light-transmitting member.

(3) By making one of the substrate 1 or the substrate 2 an organic EL display panel, and the other an opaque member, a so-called bottom emission type organic EL display device can be manufactured.

(4) By making one of the base material 1 or base material 2 a protective panel and the other is an image display device or various substrates, it is possible to manufacture a shadow with a protective panel Like a display device or a substrate with a protective panel. In addition, one of the base material 1 or the base material 2 may be a protective panel, and the other may be a translucent member.

(5) A touch panel can be manufactured by making one of the base material 1 or the base material 2 a light-transmitting substrate on which a transparent electrode has been formed, and the other being a light-transmitting member. In addition, one of the base material 1 or the base material 2 may be a touch panel, and the other may be a translucent member.

Therefore, the manufacturing method of the laminate can be that one of the substrate 1 or the substrate 2 is a liquid crystal display panel, an organic EL display panel, a protective panel, or a touch panel, and the other is a translucent member or a non-transmitting member.

When the manufacturing method of the laminate is to combine the base material 1 and the base material 2, preferably one is an inorganic material and the other is an organic material, and more preferably glass, polyimide or a combination of these are laminated on the base material. The substrate obtained by the optical device, the composition of the substrate obtained by sequentially laminating elements such as EL and the protective film on the substrate of glass, polyimide or these combinations. The light and thermosetting resin composition at this time is preferably one suitable for the substrate of the laminated optical filter.

<Step (A)>

Step (A) is a step of using a light and thermosetting resin composition on the substrate 1 to form a curable resin composition layer.

<<How to use>>

The method of applying the composition to the substrate 1 is not particularly limited, and for example, it is a spin coater, a die coater, a metering dispenser, inkjet printing, and screen printing. Brush and gravure printing are one or more methods selected from the group, but inkjet printing is preferred. The thickness of the curable resin composition layer formed using the composition is not particularly limited. For example, it may be 10 to 500 μm, preferably 30 to 350 μm.

<Step (B)>

Step (B) is a step of bonding the base material 2 to the curable resin composition layer to obtain a bonded body. It may be that the substrate 2 is placed on the substrate 1 on which the curable resin composition layer is formed in such a manner that the curable resin composition layer is successively placed, and then the base material 1 and the base material 2 are bonded together.

The manufacturing method of the laminated body may be that the step (B) further includes a step of subjecting the laminated body formed by the base material 1, the base material 2 and the resin layer between them to a pressure treatment. Thereby, the adhesion force of the fitting body can be improved. The pressure treatment can be performed using a squeegee, a flat pressure device, or the like.

<Step (C)>

Step (C) is a step of heating and/or irradiating the bonded body with energy rays to obtain a laminated body. In the step (C), the curable resin composition layer between the base material 1 and the base material 2 is cured, and the base materials are joined to each other.

The conditions of step (C) can be the same as the aforementioned hardening by energy rays and hardening by heating. In addition, when the substrate 1 is a substrate permeable to energy rays, the curable resin composition layer can be irradiated with energy rays from the side of the substrate 1 to form a hardened resin layer, or energy rays can be irradiated from the side of the curable resin composition layer. , And form a hardened resin layer. Substrate 1 is unable to transmit energy rays In the case of the base material, the curable resin composition layer may be irradiated with energy rays from the curable resin composition layer side to form the curable resin layer. In addition, the substrate 1 may be opaque (visible light cannot pass through) but can transmit energy rays (for example, ultraviolet rays), or transparent (visible light can pass through) but cannot transmit energy rays (for example, ultraviolet rays).

The manufacturing method of the laminated body can be used for joining the base material 1 and the base material 2 when at least one of the base material 1 and the base material 2 is a translucent member. The use of the laminate is as an image display device such as liquid crystal. In addition, the laminate can be used for joining the base material 1 and the base material 2 when the base material 1 and the base material 2 are formed simultaneously with opaque members, opaque elements, filters, and the like. The use of the laminate is as an image display device such as organic EL.

Example

The following examples will illustrate the present invention in more detail, but the present invention is not limited to these examples. Unless otherwise specified in the table, it means parts by mass and% by mass.

[Preparation of curable resin composition]

After weighing the components other than the thermal radical polymerization initiator in component A, component B, and component C in a container (material SUS) according to the addition ratio described in each table, use the Three One motor at 60~80°C and atmospheric pressure ( (Manufactured by Shinto Science Co.)) Stir at 200 revolutions/min for 30 minutes to 1 hour. Secondly, after confirming that the temperature of the composition has returned to 25°C, the thermal radical polymerization initiator is weighed out and mixed uniformly using a Three One motor at atmospheric pressure and 25°C to prepare an example Light or thermosetting resin composition of 1 to 12 and Comparative Examples 1 to 4.

[Measurement of physical properties]

Using the curable resin composition, the characteristics were measured by the following methods.

(Viscosity)

Using a viscometer (RE105U: manufactured by Toki Sangyo Co., Ltd.), an appropriate cone plate and rotation speed were selected at atmospheric pressure and 25°C to measure the viscosity of the liquid photocurable resin composition.

(Tear test)

A glass slide is used for the inorganic substrate, and a PI (polyimide) film is used for the organic material. Drop 0.2 g of the curable resin composition described in Table 1 to Table 3 on a glass slide (S1127 manufactured by Songlang Glass Co., Ltd.), and bond it to a PI film cut into 3×10 cm (Caputon manufactured by Donglei Co., Ltd., thick After 50 μm), apply about 1 kg with a squeegee (SN-print, squeegee No. 1) while going back and forth above the film 5 times to spread the liquid on the substrate. After that, a metal halide lamp (ECS-301 manufactured by Aigula) was used to ^{irradiate 3000mJ/cm 2} of light on Examples 1 to 3, 7, 9 and 11 with the addition of a photoradical polymerization initiator, and Comparative Examples 1 and 2 The curable resin composition makes it harden. Use an oven (LC113 manufactured by ESPEC) to heat at 100°C for 30 minutes to harden the curable resin composition of Examples 4-6, 8, 10, and 12 with the addition of a thermal radical polymerization initiator, and Comparative Examples 3 and 4 . Using these test pieces, a 180° peel test was performed with a tensile tester (TG-2kV manufactured by Minabe) at a tensile speed of 60 mm/min. Calculate the average value of about 40mm peeled off.

The results are shown in Table 1 to Table 3.

(A) (Meth) acrylic oligomer

(a-1): UA10000B: Polyether urethane acrylate oligomer (molecular weight 25,000, manufactured by KSM Co., Ltd.)

(a-2): UN7700: Polyester-based urethane acrylate oligomer (molecular weight 20,000, manufactured by Negami Kogyo Co., Ltd.)

(a-3): EB230: Aliphatic urethane acrylate oligomer (molecule 5,000, manufactured by Decher Co., Ltd.)

(a-4): UV6300B: Urethane acrylate oligomer (molecular weight 3,000, manufactured by Nippon Synthetic Chemical Co., Ltd.)

(a-5): TE2000: Polybutadiene-based urethane acrylate oligomer (molecular weight 3,000, manufactured by Soda Co., Ltd.)

(B) (Meth) acrylic monomer

(b-1): IBOA: Isobornyl acrylate (viscosity 7.7mPa˙s, Osaka Organic Chemical Industry Co., Ltd.)

(b-2): 4HBA: 4-hydroxybutyl acrylate (viscosity 5.5mPa˙s, Osaka Organic Chemical Industry Co., Ltd.)

(b-3): L-A: Lauryl Acrylate (Viscosity 4.0mPa˙s, Osaka Organic Chemical Industry Co., Ltd.)

(b-4): IOAA: Isooctyl acrylate (viscosity 2mPa˙s, Osaka Organic Chemical Industry Co., Ltd.)

(C) Free radical polymerization initiator

(c-1) I-184: 1-hydroxy-cyclohexyl-phenyl-ketone (photo-radical polymerization initiator, manufactured by BASF)

(c-2) Paoku O: t-butylperoxy 2-ethylhexanoate (thermal radical polymerization initiator, manufactured by Nippon Oil & Fat Co., Ltd.)

When the composition of Examples 1 to 12 is used to bond the inorganic substrate and the organic substrate, higher peel strength and excellent adhesion between the inorganic substrate and the organic substrate can be obtained.

In particular, comparing Examples 1 to 3 and Examples 4 to 6, as a result, the molecular weight of the oligomer is further increased, and the peel strength is further improved.

When comparing Examples 1 and 4, Comparative Examples 2 and 5, and Comparative Examples 3 and 6, as a result, the peel strength can be further improved by thermal hardening. When comparing Examples 2 and 7, Examples 5 and 8, Examples 3 and 9, and Examples 6 and 10, the result will be that the content of component A is less, and the peel strength is further improved.

Comparing Examples 3 and 11, and Comparative Examples 6 and 12, the result is that component B contains a "short and branched alkyl chain" (meth)acrylic group. The composition of the body can further improve the peel strength when compared with the composition containing the "longer and linear alkyl chain" (meth)acrylic monomer.

Since Comparative Examples 1 to 4 use oligomers with a molecular weight of 3,000, the peel strength is low, and the adhesion between the inorganic substrate and the organic substrate is poor.

Industrial use possibility

Since the composition can have excellent adhesion between inorganic materials and organic materials, it can be used as an adhesive preferably for bonding substrates for inkjet coating to each other, and has high industrial applicability.

Claims (7)

A curable resin composition characterized by containing a (meth)acrylic oligomer (component A) with a molecular weight of 5,000 or more, a (meth)acrylic monomer (component B), and a photo-radical polymerization initiator And at least one kind of radical polymerization initiator selected from the group of thermal radical polymerization initiators (component C), component B is a (meth)acrylate containing alicyclic (meth)acrylate and hydroxyl group And branched C ₆ ~C ₁₆ alkyl (meth)acrylate, and the viscosity is below 150mPa˙s. Such as the curable resin composition of claim 1, wherein component B is (meth)acrylate containing less than 10 mPa˙s. The curable resin composition of claim 1 or 2, wherein the component A is 30 parts by weight or less with respect to 100 parts by weight of the total of the component A and the component B. Such as the curable resin composition of claim 1 or 2, which is an adhesive. Such as the curable resin composition of claim 3, which is an adhesive. Such as the curable resin composition of claim 1 or 2, which is used in a group selected from a group of spin coaters, die coaters, quantitative dispensers, inkjet coating, screen printing, and gravure printing More than one method. For example, the curable resin composition of claim 3, which is used for one or more selected from a group of spin coaters, die coaters, quantitative dispensers, inkjet printing, screen printing, and gravure printing method.