Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/55—Boron-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/06—Polymers provided for in subclass C08G
  • C08F290/067—Polyurethanes; Polyureas
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/06—Polymers provided for in subclass C08G
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/38—Boron-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
  • C08K5/092—Polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/13—Phenols; Phenolates
  • C08K5/134—Phenols containing ester groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/52—Phosphorus bound to oxygen only
  • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
  • C08L75/04—Polyurethanes
  • C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
  • C08L75/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/38—Boron-containing compounds
  • C08K2003/387—Borates

Definitions

• the present disclosure relates to polymerizable compositions and the like.
• Patent Document 1 describes a thermosetting composition containing a polymerizable compound.
• the polymerizable composition is thermally cured near a member that should not be exposed to high heat, the polymerizable composition that has come into contact with a member that should not be exposed to high heat is There are cases where things are hardened by heat. In these cases, the polymerizable composition is required to have a lower reaction initiation temperature in order to avoid deterioration of the member by performing thermosetting at a low temperature.
• One aspect of the present disclosure aims to provide a polymerizable composition that can lower the reaction initiation temperature.
• the present disclosure relates to the following [1] to [11].
• a polymerizable composition containing a polymerizable compound comprising (A) a borate anion, (B) an aromatic carboxylic acid having two or more hydroxy groups, a salt of the aromatic carboxylic acid, and the above-mentioned A polymerizable composition containing at least one member selected from the group consisting of hydrates of aromatic carboxylic acids.
• the component (A) contains a borate anion having a naphthalene ring.
• the numerical range indicated by “ ⁇ ” indicates a range including the numerical values described before and after “ ⁇ ” as the minimum and maximum values, respectively.
• “A or more” in the numerical range means a range exceeding A and A.
• “A or less” in the numerical range means a range less than A and A.
• the upper limit or lower limit of a numerical range of a certain stage can be arbitrarily combined with the upper limit or lower limit of a numerical range of another stage.
• the upper limit or lower limit of the numerical range may be replaced with a value shown in the examples.
• “A or B” may include either A or B, or may include both.
• the materials exemplified in this specification may be used alone or in combination of two or more types.
• the content of each component in the composition means the total amount of the multiple substances present in the composition, unless otherwise specified.
• (Meth)acrylate means at least one of acrylate and the corresponding methacrylate. The same applies to other similar expressions such as “(meth)acrylic”.
• the content of (meth)acrylate compounds means the total amount of acrylate compounds and methacrylate compounds.
• the "alkyl group” may be linear, branched, or cyclic unless otherwise specified.
• the "hydroxy group” does not include the OH group contained in the carboxy group.
• total mass of the polymerizable composition refers to the total mass of the solid content of the polymerizable composition.
• the solid content of the polymerizable composition refers to the non-volatile content excluding volatile content (water, organic solvent, etc.) that can be volatilized.
• the solid content refers to the components that remain without volatilization when the polymerizable composition is dried, and includes components that are liquid, syrup-like, wax-like, etc. at 25°C.
• the "weight average molecular weight” can be measured by gel permeation chromatography (GPC) under the following measurement conditions and by conversion from a calibration curve using standard polystyrene.
• GPC gel permeation chromatography
• Equipment Tosoh Corporation, GPC-8020 Detector: Tosoh Corporation, RI-8020 Column: Showa Denko Materials Co., Ltd., Gelpack GL-A-160-S+GL-A150 Sample concentration: 120mg/3mL
• Solvent Tetrahydrofuran Injection volume: 60 ⁇ L Pressure: 294 ⁇ 10 6 Pa (30 kgf/cm 2 ) Flow rate: 1.00mL/min
• the polymerizable composition according to the present embodiment is a polymerizable composition containing a polymerizable compound, and includes (A) a borate anion (hereinafter referred to as "component (A)” in some cases) and (B) two or more At least one type selected from the group consisting of an aromatic carboxylic acid having a hydroxy group, a salt of the aromatic carboxylic acid, and a hydrate of the aromatic carboxylic acid (hereinafter referred to as "component (B)” in some cases) Contains and.
• component (A) a borate anion
• component (B) two or more At least one type selected from the group consisting of an aromatic carboxylic acid having a hydroxy group, a salt of the aromatic carboxylic acid, and a hydrate of the aromatic carboxylic acid
• component (B) a hydrate of the aromatic carboxylic acid
• the polymerizable composition according to the present embodiment contains at least one kind of polymerizable compound, and as the polymerizable compound, at least one kind selected from the group consisting of a compound containing component (A) and component (B). It may contain a polymerizable compound that does not fall under at least one selected from the group consisting of a compound containing component (A) and component (B).
• the polymerizable composition according to this embodiment includes a compound containing component (A), and , and (B) may contain at least one polymerizable compound that does not fall under the group consisting of components.
• the polymerizable composition according to this embodiment can be used as a thermosetting polymerizable composition.
• the reaction initiation temperature can be lowered.
• the polymerizable composition according to the present embodiment in the evaluation method described in the Examples below, for example, 84.00°C or less (preferably 80.00°C or less, 75.00°C or less, 70.00°C
• the following reaction initiation temperatures can be obtained:
• the reaction initiation temperature is low when the polymerizable composition (for example, a film-like polymerizable composition) is stored.
• the reaction initiation temperature can be prevented from increasing.
• 20.00% or less preferably 15.00% or less, 10.00% or less, 5% .00% or less
• Applications of the polymerizable composition according to the present embodiment are not particularly limited, and include display devices, semiconductor devices, members for electronic devices, and the like.
• the polymerizable composition according to the present embodiment may be used in micro LEDs (Light Emitting Diodes), micro OLEDs (Organic Light Emitting Diodes), and the like.
• the polymerizable composition according to this embodiment contains a borate anion as the component (A).
• the polymerizable composition according to the present embodiment may contain a boron salt containing a borate anion (salt of component (A) and a counter cation of component (A); hereinafter referred to as "component (a1)").
• component (a1) a boron salt containing a borate anion (salt of component (A) and a counter cation of component (A); hereinafter referred to as "component (a1)").
• the component (A) may be bound to the counter cation, or may be free without binding to the counter cation.
• the number of boron atoms may be 1 to 4, 1 to 3, or 1 to 2 from the viewpoint of easily lowering the reaction initiation temperature.
• Component (A) may contain a borate anion having a naphthalene ring (substituted or unsubstituted naphthyl group) from the viewpoint of easily lowering the reaction initiation temperature, and may contain a borate anion having a naphthalene ring (substituted or unsubstituted naphthyl group) bonded to a boron atom. group), may contain at least one selected from the group consisting of alkyltriarylborate anions and tetraarylborate anions, may contain alkyltriarylborate anions, and may contain alkyltrinaphthylborate anions. may include a butyltrinaphthylborate anion, and may include an n-butyltrinaphthylborate anion.
• the number of naphthalene rings (number in one molecule) or the number of naphthalene rings (number in one molecule) bonded to the boron atom is set from 1 to 1, from the viewpoint of easily lowering the reaction initiation temperature. It may be 4, 1-3, 2-4, 2-3, or 3-4, and may be 3.
• Component (A) may have an unsubstituted naphthalene ring or a naphthalene ring having a substituent.
• substituent include a halogen atom, an alkyl group, an aryl group, an alkoxy group, and the like.
• Component (A) may have an alkyl group bonded to a boron atom from the viewpoint of easily lowering the reaction initiation temperature.
• the number of alkyl groups bonded to the boron atom may be 1 to 3 or 1 to 2 from the viewpoint of easily lowering the reaction initiation temperature.
• the number of carbon atoms in the alkyl group bonded to the boron atom may be in the following range from the viewpoint of easily lowering the reaction initiation temperature.
• the number of carbon atoms in the alkyl group may be 1 or more, 2 or more, 3 or more, or 4 or more.
• the number of carbon atoms in the alkyl group may be 12 or less, 10 or less, 8 or less, 6 or less, 5 or less, or 4 or less. From these viewpoints, the number of carbon atoms in the alkyl group is 1-12, 1-8, 1-4, 2-12, 2-8, 2-4, 3-12, 3-8, 3-4, 4- It may be 12, or 4 to 8.
• Component (A) may have a functional group other than a naphthalene ring (naphthyl group) and an alkyl group as a functional group bonded to a boron atom.
• functional groups include aryl groups other than naphthyl groups (for example, phenyl groups).
• Counter cations in component (a1) include quaternary ammonium ions, tertiary ammonium ions, secondary ammonium ions, primary ammonium ions, ammonium ions, imidazolium ions, imidazolinium ions, pyridinium ions, alkali Examples include metal ions (sodium ions, potassium ions, etc.), phosphonium cations, sulfonium cations, iodonium cations, and the like. Component (a1) may not contain metal ions or may contain metal ions. Examples of metal ions include alkali metal ions (sodium ions, potassium ions, etc.). Component (a1) may contain a quaternary ammonium ion as a countercation from the viewpoint of easily lowering the reaction initiation temperature.
• examples of the substituent bonded to the nitrogen atom include an alkyl group, an aryl group (for example, a phenyl group), and the like.
• Component (a1) may contain, as a countercation, a quaternary ammonium ion having an alkyl group bonded to a nitrogen atom, and a linear alkyl group bonded to a nitrogen atom, from the viewpoint of easily lowering the reaction initiation temperature. , and a quaternary ammonium ion having at least one selected from the group consisting of a branched alkyl group bonded to a nitrogen atom.
• the number of carbon atoms in the alkyl group bonded to the nitrogen atom may be in the following range from the viewpoint of easily lowering the reaction initiation temperature.
• the number of carbon atoms in the alkyl group may be 1 or more, 2 or more, 3 or more, or 4 or more.
• the number of carbon atoms in the alkyl group may be 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, 5 or less, or 4 or less. From these viewpoints, the number of carbon atoms in the alkyl group may be 1 to 18, 1 to 8, 1 to 4, 2 to 6, 4 to 18, or 4 to 8.
• quaternary ammonium ions include tetraalkylammonium ions, trialkylammonium ions, dialkylammonium ions, monoalkylammonium ions, tetraarylammonium ions, triarylammonium ions, diarylammonium ions, monoarylammonium ions, and the like.
• Component (a1) may contain a tetraalkylammonium ion as a countercation from the viewpoint of easily lowering the reaction initiation temperature.
• tetraalkylammonium ion examples include tetramethylammonium ion, tetraethylammonium ion, tetrapropylammonium ion, tetrabutylammonium ion (e.g., tetra n-butylammonium ion), tetrahexylammonium ion, triethylmethylammonium ion, tributylethylammonium ion, Examples include trimethyldecylammonium ion.
• Component (a1) may contain a tetrabutylammonium ion as a countercation from the viewpoint of easily lowering the reaction initiation temperature.
• the content of component (a1) may be in the following range based on the total mass of the polymerizable composition.
• the content of component (a1) is 0.01% by mass or more, 0.05% by mass or more, 0.10% by mass or more, 0.20% by mass or more, 0.30% by mass or more, from the viewpoint of easily lowering the reaction initiation temperature.
• the content of component (a1) is 20.00% by mass or less, 15.00% by mass or less, 10.00% by mass or less, 8.00% by mass or less, 7.00% by mass or less % or less, 6.00 mass% or less, 5.00 mass% or less, 4.00 mass% or less, 3.00 mass% or less, 2.00 mass% or less, 1.50 mass% or less, 1.20 mass% 1.10% by mass or less, 1.00% by mass or less, 0.90% by mass or less, 0.80% by mass or less, 0.70% by mass or less, 0.60% by mass or less, 0.50% by mass or less , or 0.40% by mass or less.
• the content of component (a1) is 0.01 to 20.00% by mass, 0.30 to 20.00% by mass, 0.70 to 20.00% by mass, and 1.00 to 20.0% by mass.
• the polymerizable composition according to the present embodiment includes at least one type selected from the group consisting of aromatic carboxylic acid b, a salt of aromatic carboxylic acid b, and a hydrate of aromatic carboxylic acid b, as component (B). (However, excluding compounds corresponding to component (a1)).
• the salts of aromatic carboxylic acid b include alkali metal salts such as sodium salts and potassium salts.
• At least one type selected from the group consisting of aromatic carboxylic acid b, a salt of aromatic carboxylic acid b, and a hydrate of aromatic carboxylic acid b is an aromatic It may be at least one selected from the group consisting of group carboxylic acids b and hydrates of aromatic carboxylic acids b, and may be aromatic carboxylic acids b.
• Aromatic carboxylic acid b has at least one aromatic ring.
• the number of aromatic rings (number in one molecule) may be 1 from the viewpoint of easily lowering the reaction initiation temperature.
• Examples of the aromatic ring include a benzene ring and a naphthalene ring.
• the aromatic carboxylic acid b may contain an aromatic carboxylic acid having a benzene ring from the viewpoint of easily lowering the reaction initiation temperature.
• Aromatic carboxylic acid b has a carboxy group bonded to an aromatic ring.
• Aromatic carboxylic acid b is an aromatic carboxylic acid having a hydroxy group (phenolic hydroxyl group) bonded to an aromatic ring, from the viewpoint of easily lowering the reaction initiation temperature and from the viewpoint of easily obtaining excellent storage stability regarding the reaction initiation temperature. May contain acids.
• Aromatic carboxylic acid b is a hydroxy group bonded to the para position relative to the carboxy group bonded to the aromatic ring, from the viewpoint of easily lowering the reaction initiation temperature and from the viewpoint of easily obtaining excellent storage stability regarding the reaction initiation temperature. It may have one or two hydroxy groups bonded to the meta position to the carboxy group bonded to the aromatic ring.
• the number of carboxy groups bonded to the aromatic ring (number in one molecule) is determined from the viewpoint of easily lowering the reaction initiation temperature and from the viewpoint of easily obtaining excellent storage stability regarding the reaction initiation temperature.
• the number of hydroxy groups (number in one molecule) or the number of hydroxy groups (number in one molecule) bonded to the aromatic ring is determined from the viewpoint of easily lowering the reaction initiation temperature, and From the viewpoint of easily obtaining excellent storage stability regarding the reaction initiation temperature, it may be 1 to 4, 1 to 3, 1 to 2, 2 to 4, 2 to 3, or 3 to 4, or 2. , 3.
• the aromatic ring of the aromatic carboxylic acid b may have a substituent other than a carboxy group and a hydroxy group, or may not have a substituent other than a carboxy group and a hydroxy group.
• substituents include an alkyl group and an alkoxy group.
• Aromatic carboxylic acids b include 3,4-dihydroxybenzoic acid (protocatechuic acid), 3,5-dihydroxybenzoic acid ( ⁇ -resorcylic acid), 2,4-dihydroxybenzoic acid ( ⁇ -resorcylic acid), 2, 6-dihydroxybenzoic acid ( ⁇ -resorcilic acid), 2,3-dihydroxybenzoic acid (2-pyrocatechuic acid), 2,5-dihydroxybenzoic acid (gentisic acid), 2,4-dihydroxy-6-methylbenzoic acid ( (orceric acid), 3,4,5-trihydroxybenzoic acid (gallic acid), phloroglucinol carboxylic acid, and the like.
• Aromatic carboxylic acid b is 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 2 , 3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, and 3,4,5-trihydroxybenzoic acid. It may contain at least one selected from the group consisting of 3,4-dihydroxybenzoic acid (protocatechuic acid) and 3,4,5-trihydroxybenzoic acid (gallic acid).
• the content of component (B) is the sum of the aromatic carboxylic acid, aromatic carboxylic acid salt, and aromatic carboxylic acid hydrate contained in the polymerizable composition from the viewpoint of easily lowering the reaction initiation temperature. Based on the amount, 50.00% by mass or more, more than 50.00% by mass, 70.00% by mass or more, 80.00% by mass or more, 90.00% by mass or more, 92.00% by mass or more, 95.00 It may be greater than or equal to 97.00% by weight, greater than or equal to 98.00% by weight, greater than or equal to 99.00% by weight, or substantially 100.00% by weight.
• the content of component (B) may be in the following range based on the total mass of the polymerizable composition.
• the content of component (B) is 0.01% by mass or more, 0.05% by mass or more, 0.10% by mass or more, 0.30% by mass or more, 0.50% by mass or more, from the viewpoint of easily lowering the reaction initiation temperature.
• Mass% or more, 0.80 mass% or more 1.00 mass% or more, 1.20 mass% or more, 1.30 mass% or more, 1.40 mass% or more, 1.50 mass% or more, 1.60 mass% % or more, 1.80% by mass or more, or 2.00% by mass or more.
• the content of component (B) is 10.00% by mass or less, 8.00% by mass or less, 6.00% by mass or less, 5.00% by mass from the viewpoint of easily obtaining excellent storage stability regarding the reaction initiation temperature. 4.00% by mass or less, 3.00% by mass or less, 2.50% by mass or less, 2.00% by mass or less, 1.80% by mass or less, 1.60% by mass or less, 1.50% by mass or less , or 1.40% by mass or less. From these viewpoints, the content of component (B) is 0.01 to 10.00% by mass, 0.01 to 2.50% by mass, 0.01 to 2.00% by mass, and 1.00 to 10.0% by mass. 00% by mass, 1.00-2.50% by mass, 1.00-2.00% by mass, 1.50-10.00% by mass, 1.50-2.50% by mass, or 1.50-2.50% by mass It may be 2.00% by mass.
• the mass ratio R1 of the content of component (B) to the content of component (a1) (component (B)/component (a1)) may be in the following range from the viewpoint of easily lowering the reaction initiation temperature.
• Mass ratio R1 is 0.01 or more, 0.05 or more, 0.10 or more, 0.30 or more, 0.50 or more, 0.80 or more, 1.00 or more, 1.20 or more, 1.50 or more, It may be 1.80 or more, 2.00 or more, 2.50 or more, 3.00 or more, 3.50 or more, 4.00 or more, or 5.00 or more.
• the mass ratio R1 is 10.00 or less, 8.00 or less, 6.00 or less, 5.00 or less, 4.00 or less, 3.50 or less, from the viewpoint of easily obtaining excellent storage stability regarding the reaction initiation temperature. It may be 3.00 or less, 2.50 or less, 2.00 or less, 1.80 or less, 1.50 or less, or 1.20 or less. From these viewpoints, the mass ratio R1 is 0.01 to 10.00, 0.01 to 6.00, 0.01 to 3.00, 0.01 to 1.50, 1.00 to 10.00, 1.00-6.00, 1.00-3.00, 1.00-1.50, 1.50-10.00, 1.50-6.00, or 1.50-3.00 It's good to be there.
• the polymerizable composition according to the present embodiment may contain a polymerizable compound as component (C) (excluding compounds corresponding to component (a1) or component (B)).
• component (C) examples include radical polymerizable compounds, cationic polymerizable compounds, anionic polymerizable compounds, and the like.
• Component (C) may contain a radically polymerizable compound from the viewpoint of easily lowering the reaction initiation temperature.
• Component (C) includes (meth)acrylate compounds, maleimide compounds, vinyl ether compounds, allyl compounds, styrene compounds, (meth)acrylamide compounds, nadimide compounds, natural rubber, isoprene rubber, butyl rubber, nitrile rubber, butadiene rubber, and styrene rubber. Examples include butadiene rubber, acrylonitrile-butadiene rubber, carboxylated nitrile rubber, epoxy compounds, oxetane compounds, lactone compounds, and the like.
• Component (C) may contain a compound having an ethylenically unsaturated bond and may contain a (meth)acrylate compound from the viewpoint of easily lowering the reaction initiation temperature.
• (Meth)acrylate compounds include (poly)urethane (meth)acrylate, epoxy (meth)acrylate, methyl (meth)acrylate, polyether (meth)acrylate, polyester (meth)acrylate, polybutadiene (meth)acrylate, silicone ( meth)acrylate, ethyl(meth)acrylate, 2-cyanoethyl(meth)acrylate, 2-(2-ethoxyethoxy)ethyl(meth)acrylate, 2-ethoxyethyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, n -Hexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, isopropyl (meth)acrylate, hydroxypropyl (meth)acrylate, isobutyl (meth)acrylate, isobornyl (meth)acrylate, isodecyl (meth)acrylate, isooctyl (meth)
• Polyurethane (meth)acrylate and “urethane (meth)acrylate” are collectively referred to as “(poly)urethane (meth)acrylate.”
• Component (C) may include a bifunctional (meth)acrylate compound.
• Component (C) may contain a urethane (meth)acrylate compound having a polycarbonate skeleton (hereinafter referred to as "component (c1)") from the viewpoint of easily lowering the reaction initiation temperature, and may include a urethane (meth)acrylate compound having a structure derived from a polycarbonate polyol. It may contain a (meth)acrylate compound, and may contain a compound represented by the following general formula (c1).
• R 1 represents a hydrogen atom or a methyl group
• j represents an integer of 1 to 3
• k represents an integer of 2 to 7
• m represents an integer of 1 to 8
• n represents an integer of 5 to 7. indicates an integer.
• j may be 1 to 2 or 2 to 3
• k may be 2 to 3 or 3 to 5
• m may be 1 to 6.
• 1-4 or 1-2 may be 5-6 or 6-7.
• the weight average molecular weight of component (c1) is 1,000 or more, 3,000 or more, 5,000 or more, 8,000 or more, 10,000 or more, 12,000 or more, 13,000 or more, 14,000 or more, or 15,000 or more, from the viewpoint of easily lowering the reaction initiation temperature. It's fine.
• the weight average molecular weight of the component (c1) may be 100,000 or less, 50,000 or less, 30,000 or less, 25,000 or less, 20,000 or less, 18,000 or less, or 15,000 or less, from the viewpoint of easily lowering the reaction initiation temperature. From these viewpoints, the weight average molecular weight of component (c1) may be 1,000 to 100,000, 5,000 to 50,000, or 10,000 to 30,000.
• the content of component (c1) may be in the following range based on the total mass of component (C) from the viewpoint of easily lowering the reaction initiation temperature.
• the content of component (c1) is 10.00% by mass or more, 15.00% by mass or more, 20.00% by mass or more, 25.00% by mass or more, 30.00% by mass or more, 35.00% by mass or more , 40.00% by mass or more, 45.00% by mass or more, 50.00% by mass or more, or 55.00% by mass or more.
• the content of component (c1) is 90.00% by mass or less, 85.00% by mass or less, 80.00% by mass or less, 75.00% by mass or less, 70.00% by mass or less, 65.00% by mass or less , or 60.00% by mass or less. From these viewpoints, the content of component (c1) is 10.00 to 90.00% by mass, 10.00 to 80.00% by mass, 10.00 to 70.00% by mass, and 20.00 to 90.0% by mass. 00% by mass, 20.00-80.00% by mass, 20.00-70.00% by mass, 40.00-90.00% by mass, 40.00-80.00% by mass, or 40.00- It may be 70.00% by mass.
• the content of component (c1) may be in the following range based on the total mass of the polymerizable composition from the viewpoint of easily lowering the reaction initiation temperature.
• the content of component (c1) may be 5.00% by mass or more, 10.00% by mass or more, 15.00% by mass or more, or 20.00% by mass or more.
• the content of component (c1) is 50.00% by mass or less, 45.00% by mass or less, 40.00% by mass or less, 35.00% by mass or less, 30.00% by mass or less, or 25.00% by mass % or less. From these viewpoints, the content of component (c1) is 5.00 to 50.00% by mass, 5.00 to 40.00% by mass, 5.00 to 30.00% by mass, and 10.00 to 50.0% by mass. 00% by mass, 10.00 - 40.00% by mass, 10.00 - 30.00% by mass, 20.00 - 50.00% by mass, 20.00 - 40.00% by mass, or 20.00 - It may be 30.00% by weight.
• Component (C) does not contain isocyanuric acid alkylene oxide-modified di(meth)acrylate (excluding compounds corresponding to component (c1); hereinafter referred to as “component (c2)”) from the viewpoint of easily lowering the reaction initiation temperature. and may include isocyanuric acid ethylene oxide modified di(meth)acrylate.
• the content of component (c2) may be in the following range based on the total mass of component (C) from the viewpoint of easily lowering the reaction initiation temperature.
• the content of component (c2) may be 1.00% by mass or more, 5.00% by mass or more, 10.00% by mass or more, 15.00% by mass or more, or 20.00% by mass or more.
• the content of component (c2) is 50.00% by mass or less, 45.00% by mass or less, 40.00% by mass or less, 35.00% by mass or less, 30.00% by mass or less, or 25.00% by mass % or less.
• component (c2) is 1.00 to 50.00% by mass, 1.00 to 40.00% by mass, 1.00 to 30.00% by mass, and 10.00 to 50.0% by mass. 00% by mass, 10.00 - 40.00% by mass, 10.00 - 30.00% by mass, 20.00 - 50.00% by mass, 20.00 - 40.00% by mass, or 20.00 - It may be 30.00% by weight.
• the content of component (c2) may be in the following range based on the total mass of the polymerizable composition from the viewpoint of easily lowering the reaction initiation temperature.
• the content of component (c2) may be 1.00% by mass or more, 3.00% by mass or more, 5.00% by mass or more, 8.00% by mass or more, or 9.00% by mass or more.
• the content of component (c2) may be 30.00% by mass or less, 25.00% by mass or less, 20.00% by mass or less, 15.00% by mass or less, or 10.00% by mass or less. From these viewpoints, the content of component (c2) is 1.00 to 30.00% by mass, 1.00 to 20.00% by mass, 1.00 to 10.00% by mass, and 5.00 to 30.0% by mass.
• component (C) is a di(meth)acrylate compound (component (c1) or (c2 (hereinafter referred to as “component (c3)”)), from the group consisting of dimethylol tricyclodecane di(meth)acrylate and tricyclodecane diol di(meth)acrylate. It may contain at least one selected one.
• the content of component (c3) may be in the following range based on the total mass of component (C) from the viewpoint of easily lowering the reaction initiation temperature.
• the content of component (c3) may be 1.00% by mass or more, 5.00% by mass or more, 10.00% by mass or more, 15.00% by mass or more, or 20.00% by mass or more.
• the content of component (c3) is 50.00% by mass or less, 45.00% by mass or less, 40.00% by mass or less, 35.00% by mass or less, 30.00% by mass or less, or 25.00% by mass or less % or less.
• the content of component (c3) is 1.00 to 50.00% by mass, 1.00 to 40.00% by mass, 1.00 to 30.00% by mass, and 10.00 to 50.0% by mass. 00% by mass, 10.00 - 40.00% by mass, 10.00 - 30.00% by mass, 20.00 - 50.00% by mass, 20.00 - 40.00% by mass, or 20.00 - It may be 30.00% by weight.
• the content of component (c3) may be in the following range based on the total mass of the polymerizable composition from the viewpoint of easily lowering the reaction initiation temperature.
• the content of component (c3) may be 1.00% by mass or more, 3.00% by mass or more, 5.00% by mass or more, 8.00% by mass or more, or 9.00% by mass or more.
• the content of component (c3) may be 30.00% by mass or less, 25.00% by mass or less, 20.00% by mass or less, 15.00% by mass or less, or 10.00% by mass or less. From these viewpoints, the content of component (c3) is 1.00 to 30.00% by mass, 1.00 to 20.00% by mass, 1.00 to 10.00% by mass, and 5.00 to 30.0% by mass.
• the content of component (C) may be in the following range based on the total mass of the polymerizable composition from the viewpoint of easily lowering the reaction initiation temperature.
• the content of component (C) is 10.00% by mass or more, 15.00% by mass or more, 20.00% by mass or more, 25.00% by mass or more, 30.00% by mass or more, 35.00% by mass or more , or 40.00% by mass or more.
• the content of component (C) is 80.00% by mass or less, 75.00% by mass or less, 70.00% by mass or less, 65.00% by mass or less, 60.00% by mass or less, 55.00% by mass or less , 50.00% by mass or less, or 45.00% by mass or less.
• component (C) is 10.00 to 80.00% by mass, 10.00 to 60.00% by mass, 10.00 to 50.00% by mass, and 30.00 to 80.00% by mass. 00% by mass, 30.00-60.00% by mass, 30.00-50.00% by mass, 35.00-80.00% by mass, 35.00-60.00% by mass, or 35.00- It may be 50.00% by weight.
• the mass ratio R2 of the content of component (C) to the content of component (a1) (component (C)/component (a1)) may be in the following range. From the viewpoint of adjusting the reaction initiation temperature, the mass ratio R2 is 1.00 or more, 5.00 or more, 10.00 or more, 20.00 or more, 30.00 or more, 40.00 or more, 50.00 or more, 60 It may be .00 or more, 80.00 or more, or 100.00 or more. From the viewpoint of easily lowering the reaction initiation temperature, the mass ratio R2 is 300.00 or less, 250.00 or less, 200.00 or less, 150.00 or less, 120.00 or less, 100.00 or less, 80.00 or less, It may be 60.00 or less, 50.00 or less, or 40.00 or less.
• the mass ratio R2 is 1.00 to 300.00, 1.00 to 120.00, 1.00 to 60.00, 1.00 to 40.00, 20.00 to 300.00, 20.00-120.00, 20.00-60.00, 20.00-40.00, 30.00-300.00, 30.00-120.00, 30.00-60.00, or It may be between 30.00 and 40.00.
• the mass ratio R3 of the content of component (C) to the content of component (B) (component (C)/component (B)) may be in the following range.
• the mass ratio R3 is 1.00 or more, 5.00 or more, 10.00 or more, 15.00 or more, 20.00 or more, 25.00 or more, from the viewpoint of easily obtaining excellent storage stability regarding the reaction initiation temperature. Alternatively, it may be 30.00 or more. From the viewpoint of easily lowering the reaction initiation temperature, the mass ratio R3 is 300.00 or less, 200.00 or less, 100.00 or less, 80.00 or less, 50.00 or less, 45.00 or less, 40.00 or less, It may be 35.00 or less, 30.00 or less, 25.00 or less, or 20.00 or less.
• the mass ratio R3 is 1.00 to 300.00, 1.00 to 50.00, 1.00 to 30.00, 10.00 to 300.00, 10.00 to 50.00, It may be 10.00 to 30.00, 20.00 to 300.00, 20.00 to 50.00, or 20.00 to 30.00.
• the polymerizable composition according to the present embodiment may contain a polymerization initiator (excluding compounds corresponding to component (a1), component (B), or component (C)) as component (D), It does not need to contain a polymerization initiator.
• Component (D) may include a thermal polymerization initiator.
• Component (D) includes radical polymerization initiators, cationic polymerization initiators, anionic polymerization initiators, and the like.
• Component (D) may contain a radical polymerization initiator from the viewpoint of easily lowering the reaction initiation temperature.
• Component (D) includes ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, and methyl cyclohexanone peroxide; 1,1-bis(tert-butylperoxy)cyclohexane, 1,1-bis(tert-butylperoxy); )-2-methylcyclohexane, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-hexylperoxy)cyclohexane, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-hexylperoxy)cyclohexane, -hexylperoxy)-3,3,5-trimethylcyclohexane; hydroperoxides such as p-menthane hydroperoxide; ⁇ , ⁇ '-bis(tert-but
• Component (D) may contain a peroxide, an organic peroxide, and a diacyl peroxide from the viewpoint of easily lowering the reaction initiation temperature.
• the content of component (D) may be in the following range based on the total mass of the polymerizable composition.
• the content of component (D) is 0.10% by mass or more, 0.50% by mass or more, 1.00% by mass or more, 1.50% by mass or more, 2.00% by mass or more, from the viewpoint of easily lowering the reaction initiation temperature. It may be at least 2.50% by mass, at least 3.00% by mass, at least 3.50% by mass, at least 4.00% by mass, or at least 4.50% by mass.
• the content of component (D) is 20.00% by mass or less, 15.00% by mass or less, 10.00% by mass or less, 9.00% by mass or less, 8.00% by mass or less % or less, 7.00% by mass or less, 6.00% by mass or less, or 5.00% by mass or less. From these viewpoints, the content of component (D) is 0.10 to 20.00% by mass, 0.10 to 10.00% by mass, 0.10 to 5.00% by mass, and 1.00 to 20.0% by mass. 00% by mass, 1.00-10.00% by mass, 1.00-5.00% by mass, 3.00-20.00% by mass, 3.00-10.00% by mass, or 3.00- It may be 5.00% by mass.
• the mass ratio R4 of the content of component (D) to the content of component (a1) (component (D)/component (a1)) may be in the following range. From the viewpoint of adjusting the reaction initiation temperature, the mass ratio R4 is 0.10 or more, 0.50 or more, 1.00 or more, 2.00 or more, 3.00 or more, 4.00 or more, 5.00 or more, 6 It may be .00 or more, 8.00 or more, or 10.00 or more. From the viewpoint of easily lowering the reaction initiation temperature, the mass ratio R4 is 50.00 or less, 30.00 or less, 20.00 or less, 15.00 or less, 10.00 or less, 8.00 or less, 6.00 or less, It may be 5.00 or less, or 4.00 or less.
• the mass ratio R4 is 0.10 to 50.00, 0.10 to 15.00, 0.10 to 6.00, 0.10 to 5.00, 3.00 to 50.00, 3.00-15.00, 3.00-6.00, 3.00-5.00, 5.00-50.00, 5.00-15.00, or 5.00-6.00 It's good to be there.
• the mass ratio R5 of the content of component (D) to the content of component (B) (component (D)/component (B)) may be in the following range. Mass ratio R5 is 0.10 or more, 0.50 or more, 1.00 or more, 1.50 or more, 2.00 or more, 2.50 or more, from the viewpoint of easily obtaining excellent storage stability regarding the reaction initiation temperature. It may be 3.00 or more, or 3.50 or more. From the viewpoint of easily lowering the reaction initiation temperature, the mass ratio R5 is 50.00 or less, 30.00 or less, 20.00 or less, 15.00 or less, 10.00 or less, 8.00 or less, 5.00 or less, It may be 4.00 or less, 3.50 or less, 3.00 or less, 2.50 or less, or 2.00 or less.
• the mass ratio R5 is 0.10 to 50.00, 0.10 to 20.00, 0.10 to 3.00, 1.00 to 50.00, 1.00 to 20.00, It may be 1.00 to 3.00, 2.00 to 50.00, 2.00 to 20.00, or 2.00 to 3.00.
• the mass ratio R6 of the content of component (D) to the content of component (C) (component (D)/component (C)) may be in the following range.
• the mass ratio R6 may be 0.01 or more, 0.03 or more, 0.05 or more, 0.08 or more, or 0.10 or more from the viewpoint of easily lowering the reaction initiation temperature.
• the mass ratio R6 is 5.00 or less, 3.00 or less, 1.00 or less, 0.50 or less, 0.30 or less, 0.20 or less, or 0.15 or less, from the viewpoint of adjusting the reaction initiation temperature. It may be.
• the mass ratio R6 is 0.01 to 5.00, 0.01 to 1.00, 0.01 to 0.50, 0.05 to 5.00, 0.05 to 1.00, It may be 0.05 to 0.50, 0.10 to 5.00, 0.10 to 1.00, or 0.10 to 0.50.
• the polymerizable composition according to the present embodiment may contain a thermoplastic resin as the component (E), or may not contain a thermoplastic resin.
• Component (E) includes phenoxy resin, polyester, polyurethane (excluding polyester urethane), polyester urethane, ethylene vinyl acetate copolymer, butyral resin, and the like.
• Component (E) may contain at least one member selected from the group consisting of polyester urethane and ethylene-vinyl acetate copolymer from the viewpoint of easily lowering the reaction initiation temperature.
• the content of component (E) may be in the following range based on the total mass of the polymerizable composition from the viewpoint of easily lowering the reaction initiation temperature.
• the content of component (E) is 10.00% by mass or more, 15.00% by mass or more, 20.00% by mass or more, 25.00% by mass or more, 30.00% by mass or more, 35.00% by mass or more , 40.00% by mass or more, 45.00% by mass or more, or 50.00% by mass or more.
• the content of component (E) is 90.00% by mass or less, 85.00% by mass or less, 80.00% by mass or less, 75.00% by mass or less, 70.00% by mass or less, 65.00% by mass or less , 60.00% by mass or less, or 55.00% by mass or less. From these viewpoints, the content of component (E) is 10.00 to 90.00% by mass, 10.00 to 70.00% by mass, 10.00 to 60.00% by mass, and 30.00 to 90.0% by mass. 00% by mass, 30.00-70.00% by mass, 30.00-60.00% by mass, 40.00-90.00% by mass, 40.00-70.00% by mass, or 40.00- It may be 60.00% by mass.
• the polymerizable composition according to this embodiment may contain components other than the above-mentioned components.
• Such components include water, organic solvents, coupling agents, fillers, softeners, accelerators, deterioration inhibitors, colorants, flame retardants, thixotropic agents, and the like.
• the polymerizable composition according to the present embodiment may contain at least one of these components, or may not contain at least one of these components.
• the polymerizable composition according to this embodiment may be in the form of a film.
• the thickness of the film-like polymerizable composition or the thickness of the cured product according to this embodiment may be in the following range.
• the thickness may be 1 ⁇ m or more, 3 ⁇ m or more, 5 ⁇ m or more, 8 ⁇ m or more, 10 ⁇ m or more, 12 ⁇ m or more, 15 ⁇ m or more, 18 ⁇ m or more, or 20 ⁇ m or more.
• the thickness may be 500 ⁇ m or less, 300 ⁇ m or less, 200 ⁇ m or less, 100 ⁇ m or less, 80 ⁇ m or less, 50 ⁇ m or less, 30 ⁇ m or less, or 20 ⁇ m or less.
• the thickness may be 1 to 500 ⁇ m, 1 to 100 ⁇ m, 1 to 50 ⁇ m, 5 to 500 ⁇ m, 5 to 100 ⁇ m, 5 to 50 ⁇ m, 10 to 500 ⁇ m, 10 to 100 ⁇ m, or 10 to 50 ⁇ m. .
• polyester polyol This precipitate was washed with water and then vacuum dried to obtain a polyester polyol. After thoroughly drying this polyester polyol, it was dissolved in MEK (methyl ethyl ketone) and placed in a four-necked flask equipped with a stirrer, a dropping funnel, a reflux condenser, and a nitrogen gas introduction tube. Additionally, 0.05 parts by mass of dibutyltin dilaurate (catalyst) was added to 100 parts by mass of polyester polyol, and 50 parts by mass of 4,4'-diphenylmethane diisocyanate was added to 100 parts by mass of polyester polyol. Dissolved in MEK and added via dropping funnel. Then, polyester urethane (EU1) was obtained by stirring at 80° C. for 4 hours.
• MEK methyl ethyl ketone
• a methyl ethyl ketone solution (solid content ratio: 20% by mass) of a boron salt (tetrabutylammonium butyl trinaphthyl borate, manufactured by Showa Denko K.K., trade name: Karenz N3B), an acid component shown in Table 1, and a polymerization initiator ( A toluene solution (solid content ratio: 20% by mass) of diacyl peroxide (manufactured by NOF Corporation, trade name: Perloyl L), urethane acrylate (UA1), and isocyanuric acid ethylene oxide-modified diacrylate (manufactured by Toagosei Co., Ltd., Product name: M-215), dimethylol tricyclodecane diacrylate (manufactured by Kyoeisha Chemical Co., Ltd., product name: Light Acrylate DCP-A), and a methyl ethyl ketone
• a sexual composition was prepared.
• Table 1 shows the amounts of boron salts and acid components used (solid content, unit: parts by mass).
• the amount of 3,4,5-trihydroxybenzoic acid (gallic acid) used is the amount of 3,4,5-trihydroxybenzoic acid monohydrate used.
• the amount of polymerization initiator used (solid content) was 5.00 parts by mass, the amount of urethane acrylate (UA1) used was 25.00 parts by mass, and the amount of isocyanuric acid ethylene oxide modified diacrylate was 10.00 parts by mass.
• the amount of dimethylol tricyclodecane diacrylate used was 10.00 parts by mass
• the amount of polyester urethane (EU1) used solid content
• the amount of ethylene vinyl acetate copolymer was 7.50 parts by mass.
• 2,6-dihydroxybenzoic acid ( ⁇ -resorsilic acid) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. 3,4,5-trihydroxybenzoic acid (gallic acid) (monohydrate) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Acetic acid: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Adipic acid: Manufactured by Fuji Film Wako Pure Chemical Industries, Ltd. p-Hydroxybenzoic acid: Manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.
• reaction initiation temperature After peeling the PET film from the above-mentioned laminated film immediately after preparation, the curing exothermic behavior of the film-like polymerizable composition was measured by differential scanning calorimetry (hereinafter referred to as "DSC"), and the polymerization reaction was measured. The onset temperature of the exothermic peak was obtained as an indicator of the onset temperature. DSC measurement was performed under the following conditions to obtain a reaction initiation temperature T1.
• DSC measurement conditions Measuring device: Manufactured by PerkinElmer Japan Co., Ltd., product name “DSC8500” Sample amount: 10.0 ⁇ 0.2mg Measurement temperature range: 30-200°C Temperature increase rate: 30°C/min Measurement atmosphere: nitrogen

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