CN109071695B - Curable composition, shape-retaining coating agent, and cured product - Google Patents
Curable composition, shape-retaining coating agent, and cured product Download PDFInfo
- Publication number
- CN109071695B CN109071695B CN201780021562.6A CN201780021562A CN109071695B CN 109071695 B CN109071695 B CN 109071695B CN 201780021562 A CN201780021562 A CN 201780021562A CN 109071695 B CN109071695 B CN 109071695B
- Authority
- CN
- China
- Prior art keywords
- acrylate
- meth
- curable composition
- polyisocyanate
- hydrogenated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
-
- 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
- Paints Or Removers (AREA)
Abstract
The present invention provides: a curable composition which gives a cured product having excellent electrical insulation properties and excellent crack resistance even in a portion where photocuring is insufficient. The curable composition of the present invention comprises: a polyurethane resin (A) having a hydrogenated butadiene-based skeleton and/or a hydrogenated isoprene-based skeleton; a monofunctional (meth) acrylate (B) having an alkyl group having 10 or less carbon atoms and not containing a ring structure; and a photopolymerization initiator (C), wherein the polyurethane resin (A) is a polymer containing a polyol (a1-1) component and a polyisocyanate (a2) component, and is a polymer of monomers having an equivalent ratio (isocyanate group/hydroxyl group) within a predetermined range, and the polyisocyanate (a2) contains a polyisocyanate having an unfused 2-6 monocyclic alicyclic structure or an unfused 3-7 monocyclic aromatic ring.
Description
Technical Field
The present invention relates to a curable composition, a conformal coating agent (conformal coating agent), and a cured product.
Background
Conventionally, in the field of electronic materials, in order to protect an electronic circuit board from water, moisture, dust, and the like, an electronic circuit board after soldering is sometimes subjected to an electrical insulation treatment.
Several curable compositions for carrying out insulation treatments have been proposed. For example, patent document 1 proposes a photocurable composition used in combination with moisture curing for covering an electronic circuit, which contains: a (meth) acrylate oligomer (A) having 1 molecule thereof with an average of 1.5 or more (meth) acryloyl groups and having a diene-based or hydrogenated diene-based skeleton; a compound (B) which is a compound having 1 (meth) acryloyl group and having no isocyanate-reactive group, wherein the glass transition temperature of the homopolymer is 50 ℃ or lower; a compound (C) having 2 or more isocyanate groups; and a photopolymerization initiator (D) which does not have an isocyanate reactive group and contains components (A) to (D) in a specific ratio.
Patent document 2 proposes a photocurable drip-proof material which is used as a material for forming a coating film covering flux residue at a soldered portion, and which contains (a) hydrogenated polybutadiene acrylate, (B)1 polyisocyanate having 3 or more isocyanate groups in the molecule, (C) a reactive solvent, and (D) a photopolymerization initiator.
Patent document 3 proposes a coating agent for use in combination with one-pack type photocuring and moisture curing, which is obtained by modifying photopolymerizable (meth) acryloyl groups in an amount of 50 to 90% of the number of terminal NCO groups of a polyurethane prepolymer obtained by reacting (a) an organic polyisocyanate compound with (b) a polyester polyol containing, as a copolymerization component, at least one or more of a dimer acid, a dimer diol and a product obtained by hydrogenating the dimer acid, the polyester polyol having a number average molecular weight of 8000 or less, so that the NCO/OH ratio (a)/(b) is 1.8 to 2.3.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2014-201593
Patent document 2: japanese patent laid-open publication No. 2012-121935
Patent document 3: japanese laid-open patent publication No. 2008-159437
Disclosure of Invention
Problems to be solved by the invention
However, the photocurable composition used in combination with moisture curing of patent document 1 has the following problems: the cured product thereof has insufficient electrical insulation and transparency in the ultraviolet-irradiated portion and the ultraviolet-non-irradiated portion, and has insufficient moisture curability.
The photocurable drip-proof material of patent document 2 has the following problems: the cured product thereof has insufficient electrical insulation properties in the ultraviolet-irradiated portion and the ultraviolet-non-irradiated portion.
The coating agent used in combination with the one-pack type photocuring moisture curing of patent document 3 has the following problems: electrical insulation is insufficient in both the ultraviolet-irradiated portion and the ultraviolet-unirradiated portion of the cured product, and cracks (low crack resistance) are generated in both the ultraviolet-irradiated portion and the ultraviolet-unirradiated portion of the cured product due to expansion and contraction resulting from changes in temperature.
The present invention provides: among cured products, a curable composition using a combination of moisture curing and photo curing, which has excellent electrical insulation properties and crack resistance in both an irradiated portion and a non-irradiated portion of an active energy ray such as an ultraviolet ray, has high transparency of the cured product, and is sufficiently cured (excellent in moisture curing) even when irradiation with an active energy ray is insufficient, and a shape-retaining coating agent and a cured product using the curable composition.
Means for solving the problems
The curable composition of the present invention is characterized by comprising: a polyurethane resin (a) which has a hydrogenated butadiene-based skeleton and/or a hydrogenated isoprene-based skeleton and is a polymer containing, as monomer components, an alcohol (a1) and a polyisocyanate (a2), wherein the alcohol (a1) contains a polyol (a1-1) containing a hydrogenated polybutadiene polyol and/or a hydrogenated polyisoprene polyol, the polyurethane resin (a) is a polymer of a monomer in which the equivalent ratio (isocyanate group/hydroxyl group) of the isocyanate group in the polyisocyanate (a2) to the hydroxyl group in the alcohol (a1) is more than 1 and 8 or less, and the polyisocyanate (a2) contains a polyisocyanate having an alicyclic structure of 2 to 6 monocyclic rings or an aromatic ring of 3 to 7 monocyclic rings in one molecule;
a monofunctional (meth) acrylate (B) having an alkyl group having 10 or less carbon atoms and containing no ring structure;
and a photopolymerization initiator (C).
That is, the curable composition of the present invention is characterized by comprising: a polyurethane resin (A) having a hydrogenated butadiene-based skeleton and/or a hydrogenated isoprene-based skeleton;
a monofunctional (meth) acrylate (B) having an alkyl group having 10 or less carbon atoms and containing no ring structure; and
a photopolymerization initiator (C),
the polyurethane resin (a) is a polymer containing an alcohol (a1) and a polyisocyanate (a2) as monomer components, the alcohol (a1) includes a polyol (a1-1) containing a hydrogenated polybutadiene polyol and/or a hydrogenated polyisoprene polyol, the polyurethane resin (a) is a polymer of a monomer which includes the alcohol (a1) and the polyisocyanate (a2) and in which the equivalent ratio (isocyanate group/hydroxyl group) of the isocyanate group in the polyisocyanate (a2) to the hydroxyl group in the alcohol (a1) is greater than 1 and 8 or less, and the polyisocyanate (a2) includes a polyisocyanate having an alicyclic structure having 2 to 6 monocyclic rings or an aromatic ring having 3 to 7 monocyclic rings in one molecule.
ADVANTAGEOUS EFFECTS OF INVENTION
The curable composition of the present invention has the above-described configuration, and therefore, a cured product having excellent electrical insulation properties and having excellent crack resistance even in a portion where photocuring is insufficient can be obtained.
Detailed Description
The curable composition of the present invention comprises: a polyurethane resin (A) having a hydrogenated butadiene-based skeleton and/or a hydrogenated isoprene-based skeleton; a monofunctional (meth) acrylate (B) having an alkyl group having 10 or less carbon atoms and containing no ring structure; and a photopolymerization initiator (C).
[ polyurethane resin (A) ]
The polyurethane resin (a) has a hydrogenated butadiene-based skeleton (hydrogenated butadiene-based skeleton) and/or a hydrogenated isoprene-based skeleton (hydrogenated isoprene-based skeleton).
The urethane resin (a) is a polymer containing an alcohol (a1) and a polyisocyanate (a2) as monomer components, the alcohol (a1) including a polyol (a1-1) containing a hydrogenated polybutadiene polyol and/or a hydrogenated polyisoprene polyol. That is, the polyurethane resin (a) is a polymer of monomers containing an alcohol (a1) and a polyisocyanate (a2), the alcohol (a1) including a polyol (a1-1) containing a hydrogenated polybutadiene polyol and/or a hydrogenated polyisoprene polyol.
Examples of the hydrogenated polybutadiene polyol include hydrogenated polybutadiene diol. Hydrogenated polybutadiene diol is commercially available, for example, from Nippon Kao K.K., under the trade names "GI-1000", "GI-2000" and "GI-3000", and from Cray Valley under the trade names "Krasol HLBH-P2000" and "Krasol HLBH-P3000". The hydrogenated polybutadiene polyol may be used alone or in combination of two or more.
A part or all of unsaturated double bonds contained in a polybutadiene polyol of a hydrogenated polybutadiene polyol are hydrogenated. The degree of hydrogenation of hydrogenated polybutadiene polyol can be judged by the iodine value. The iodine value of the hydrogenated polybutadiene polyol is preferably 50 or less, more preferably 40 or less, particularly preferably 30 or less, and most preferably 25 or less. In the present invention, the iodine value is a value obtained by converting the amount of bonded halogen into the g number of iodine when 100g of the sample is reacted with halogen, and can be measured by the method specified in JIS K0070.
Examples of the hydrogenated polyisoprene polyol include hydrogenated products of polyisoprene diol. Hydrogenated polyisoprene is commercially available, for example, from Idemitsu Kosan co., ltd, under the trade name "EPOL". The hydrogenated polyisoprene polyol may be used alone or in combination of two or more.
A part or all of unsaturated double bonds contained in a polyisoprene polyol of the hydrogenated polyisoprene polyol are hydrogenated. The degree of hydrogenation of the hydrogenated polyisoprene polyol can be judged by the iodine value. The iodine value of the hydrogenated polyisoprene polyol is preferably 40 or less, more preferably 30 or less, particularly preferably 20 or less, most preferably 10 or less.
The cured product of the curable composition is excellent in electrical insulation properties, and therefore, a hydrogenated polybutadiene polyol is preferred. The cured product of the curable composition is excellent in crack resistance, and therefore, hydrogenated polyisoprene polyol is preferable.
The number average molecular weight of the polyol (a1-1) is preferably 500 to 10000, more preferably 1000 to 5000, and further preferably 2100 to 4000. When the number average molecular weight is 500 or more, the crack resistance and electrical insulation of the cured product of the curable composition are improved. When the number average molecular weight is 10000 or less, the adhesiveness of a cured product immediately after curing of the curable composition can be reduced, and the reduction in protective performance of the cured product due to adhesion of metal powder or dust in the atmosphere to the cured product can be suppressed.
The number average molecular weight of the polyol (a1-1) is a value obtained by polystyrene conversion of a molecular weight measured by Gel Permeation Chromatography (GPC). For example, the measurement can be carried out under the following measurement conditions.
The device comprises the following steps: HLC-8220GPC, manufactured by Tosoh corporation
Column: tosoh corporation
2 roots under the trade name "TSKgel SuperHZM-H
Column temperature: 40 deg.C
Eluent: tetrahydrofuran (THF)
And (3) detection: RI (Ri)
Standard curve standard polystyrene: product name of "TSKgel Standard polystyrene" manufactured by Tosoh corporation "
The content of the polyol (a1-1) component in the polyurethane resin (A) is preferably 1 to 99 mass%, more preferably 20 to 95 mass%, and particularly preferably 30 to 85 mass%.
The urethane resin (a) may contain a hydroxyl group-containing (meth) acrylate (a1-2) as a monomer component. When the urethane resin (a) contains a hydroxyl group-containing (meth) acrylate as a monomer component, a crosslinked structure of a monofunctional (meth) acrylate and, if necessary, a polyfunctional (meth) acrylate may be incorporated into the crosslinked structure formed from the urethane resin (a). Further, the cured product of the curable composition has improved appearance (transparency). The term (meth) acrylate refers to acrylate or methacrylate.
The hydroxyl group-containing (meth) acrylate (a1-2) is not particularly limited, and examples thereof include hydroxyl group-containing alkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane di (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, tris-2-hydroxyethyl isocyanurate di (meth) acrylate, glycerol di (meth) acrylate, diglycerol di (meth) acrylate, and mixtures thereof, And hydroxyl group-containing polyfunctional (meth) acrylates such as diglycerin tri (meth) acrylate and alkylene oxide (ethylene oxide, propylene oxide, etc.) adducts (including random adducts and block adducts) thereof, and pentaerythritol tri (meth) acrylate is preferred, and pentaerythritol triacrylate is more preferred. The hydroxyl group-containing (meth) acrylate (a1-2) may be used alone or in combination of two or more.
The content of the hydroxyl group-containing (meth) acrylate (a1-2) component in the polyurethane resin (a) is preferably 0.1 to 5 mass%, more preferably 0.5 to 3 mass%, and particularly preferably 0.8 to 2 mass%. When the content of the hydroxyl group-containing (meth) acrylate (a1-2) component is 0.1% by mass or more, the appearance of the cured product of the curable composition is improved. When the content of the hydroxyl group-containing (meth) acrylate (a1-2) component is 5% by mass or less, the crack resistance of the cured product of the curable composition is improved.
The content of the alcohol (a1) component in the polyurethane resin (a) is preferably 1 to 99 mass%, more preferably 20 to 95 mass%, and particularly preferably 30 to 85 mass%.
When the hydroxyl group-containing (meth) acrylate (a1-2) is contained as a monomer component of the polyurethane resin (A), the alcohol (a1) component contains the polyol (a1-1) and the hydroxyl group-containing (meth) acrylate (a 1-2).
The alcohol (a1) component may contain other alcohol components in addition to the polyol (a1-1) and the hydroxyl group-containing (meth) acrylate (a1-2) within a range not to impair the object of the present invention. Examples of the other alcohol component include polycarbonate polyol, polyester polyol, polylactone polyol, acrylic polyol, polyether polyol, polyacetal polyol, and the like. Alternatively, as the other alcohol component, a low molecular weight polyol such as ethylene glycol, diethylene glycol, 1, 4-butanediol, 1, 6-hexanediol, glycerin, trimethylolpropane, pentaerythritol, and the like can be used.
The content of the total of the polyol (a1-1) and the hydroxyl group-containing (meth) acrylate (a1-2) in the alcohol (a1) component is preferably 50% by mass or more, more preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, particularly preferably 90% by mass or more, and most preferably 100% by mass.
The polyisocyanate (a2) contains: a polyisocyanate having a plurality of isocyanate groups (-NCO) in one molecule and further having 2 to 6 monocyclic alicyclic structures or 3 to 7 monocyclic aromatic rings in one molecule. The polyisocyanate may form an isocyanurate or biuret from 3 molecules. Trimethylolpropane reacts with 3 molecules of polyisocyanate to form a trimer adduct.
Monocyclic means that the structure does not contain a polycyclic compound structure. The polycyclic compound is a compound in which 2 or more rings have 1 or more atoms in common, and specific examples thereof include a fused ring compound, a bridged ring compound, a spiro ring compound, and the like. The condensed ring compound means a compound having rings condensed at ortho-positions such as naphthalene and phenanthrene, and having rings condensed at one side such as pyrene and perylene. Bridged compounds are, for example, bicyclo [4.3.1 ]]Decane, trisRing [2.2.1.02,6]Examples of the alicyclic hydrocarbon compound include alicyclic hydrocarbon compounds obtained by fusing 2 or more rings having a ring structure in which carbons are bonded in a cyclic manner (carbon may include 1 or more heteroatoms in the ring-bonded structure) and not having aromatic properties, with each ring having a side sharing one or more atoms of 2 or more atoms. By spiro compounds are meant, for example, spiro [3.4 ]]Octane, spiro [4.5 ]]And cyclic compounds having 1 atom in a point bond (spiro bond) shared by 2 ring structures in which carbons are bonded in a cyclic manner (the carbon-bonded structure may contain 1 or more hetero atoms).
The alicyclic structure is a structure in which carbons are bonded in a cyclic manner, and does not have aromatic properties. The polyisocyanates used in the present invention may contain isocyanurate rings in the structure, but the alicyclic structure as defined herein does not contain isocyanurate rings. Carbon may contain 1 or 2 heteroatoms in the structure that is bonded in a ring. Examples of the alicyclic structure include a cycloalkane structure (cycloalkane structure) such as a cyclopropane structure, a cyclobutane structure, a cyclopentane structure, and a cyclohexane structure, a cyclobutane structure, a cyclopentene structure, a cyclohexene structure, and a cyclopropene structure, and the alicyclic structure is preferably a cycloalkane structure, more preferably a cycloalkane structure having 5 or more carbon atoms, and still more preferably a cycloalkane structure having 5 to 7 carbon atoms.
Since the cured product of the curable composition has improved electrical insulation properties, the number of alicyclic structures in one molecule of the polyisocyanate (a2) is2 to 6, preferably 2.
Examples of the polyisocyanate having an alicyclic structure with 2 to 6 monocyclic rings include: 4, 4' -dicyclohexylmethane diisocyanate (hydrogenated MDI);
biuret and isocyanurate bodies of 4, 4' -dicyclohexylmethane diisocyanate (hydrogenated MDI);
a trimer adduct of Trimethylolpropane (TMP) and hydrogenated MDI;
biuret and isocyanurate derivatives of polyisocyanates such as isophorone diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), and 1, 3-bis (isocyanatomethyl) cyclohexane (hydrogenated m-XDI);
a trimer adduct of 3 moles of any one of polyisocyanates such as isophorone diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI) and 1, 3-bis (isocyanatomethyl) cyclohexane (hydrogenated m-XDI), and 1 mole of Trimethylolpropane (TMP);
an adduct of 2 moles of Trimethylolpropane (TMP) and isophorone diisocyanate and 1 mole of Hexamethylene Diisocyanate (HDI), and the like.
Examples of the polyisocyanate having an alicyclic structure with 2 monocyclic rings include: 4,4 '-dicyclohexylmethane diisocyanate (hydrogenated MDI), an adduct of Trimethylolpropane (TMP) with 2 moles of isophorone diisocyanate and 1 mole of Hexamethylene Diisocyanate (HDI), preferably 4, 4' -dicyclohexylmethane diisocyanate (hydrogenated MDI).
The aromatic ring is a ring having aromatic properties, that is, a ring having a (4n +2) pi electron system (n is a natural number), and includes an aromatic ring containing a hetero atom. Examples of the aromatic ring include five-membered rings such as furan ring, thiophene ring, pyrrole ring, imidazole ring, thiazole ring and oxadiazole ring, six-membered rings such as benzene ring, pyridine ring and pyrazine ring, etc., preferably six-membered rings, more preferably benzene rings.
The number of aromatic rings in one molecule of the polyisocyanate (a2) is preferably 3 to 7, more preferably 3, because the cured product of the curable composition has improved electrical insulation properties.
Examples of the polyisocyanate having 3 to 7 monocyclic aromatic rings include: 4, 4', 4 "-triphenylmethane triisocyanate;
biuret and isocyanurate forms of polyisocyanates such as 1, 3-phenylene diisocyanate, 1, 4-phenylene diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, m-xylene diisocyanate, m-isocyanatophenylsulfonyl isocyanate, p-isocyanatophenylsulfonyl isocyanate, 2,4 '-diphenylmethane diisocyanate, 4' -diisocyanatobiphenyl, 3 '-dimethyl-4, 4' -diisocyanatodiphenylmethane and the like;
3 moles of any one of polyisocyanates such as 1, 3-phenylene diisocyanate, 1, 4-phenylene diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, m-xylene diisocyanate, m-isocyanatophenylsulfonyl isocyanate, p-isocyanatophenylsulfonyl isocyanate, 2,4 '-diphenylmethane diisocyanate, 4' -diisocyanatobiphenyl, 3 '-dimethyl-4, 4' -diisocyanatodiphenylmethane and the like, and a trimer adduct of 1 mole of Trimethylolpropane (TMP). Typically, the toluene diisocyanate is a mixture of 2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate.
Examples of the polyisocyanate having 3 monocyclic aromatic rings include:
4, 4', 4 "-triphenylmethane triisocyanate;
biuret and isocyanurate compounds of polyisocyanates such as 1, 3-phenylene diisocyanate, 1, 4-phenylene diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, m-xylene diisocyanate, m-isocyanatophenylsulfonyl isocyanate and p-isocyanatophenylsulfonyl isocyanate;
and a trimer adduct of 1 mole of Trimethylolpropane (TMP) and 3 moles of any one of polyisocyanates such as 1, 3-phenylene diisocyanate, 1, 4-phenylene diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, m-xylene diisocyanate, m-isocyanatophenylsulfonyl isocyanate and p-isocyanatophenylsulfonyl isocyanate, and a trimer adduct of 1 mole of trimethylolpropane and toluene diisocyanate is preferable.
The polyisocyanate used in the present invention may contain, in addition to the above-mentioned polyisocyanate, in a range not prejudicial to the object of the present invention: polyisocyanates having 1 monocyclic or polycyclic alicyclic structure, polyisocyanates having 2 or less monocyclic and/or polycyclic aromatic rings, aliphatic polyisocyanates having no ring structure, and the like.
Examples of the polyisocyanate having an alicyclic structure with 1 or more rings include isophorone diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), 2, 5-norbornane diisocyanate, 2, 6-norbornane diisocyanate and the like.
Examples of the polyisocyanate having 2 or less monocyclic and/or polycyclic aromatic rings include 4,4 ' -diphenylmethane diisocyanate (MDI), 2,4 ' -diphenylmethane diisocyanate, 4 ' -diisocyanatodiphenyl, 3 ' -dimethyl-4, 4 ' -diisocyanatodiphenyl, 1, 5-naphthalene diisocyanate, 1, 3-phenylene diisocyanate, 1, 4-phenylene diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, m-xylene diisocyanate, m-isocyanatophenylsulfonyl isocyanate, p-isocyanatophenylsulfonyl isocyanate and the like.
Examples of the aliphatic polyisocyanate having no ring structure include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,6, 11-undecanetriisocyanate, 2, 4-trimethylhexamethylene diisocyanate, 2, 6-diisocyanatomethylhexanoate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2, 6-diisocyanatohexanoate and the like.
The polyisocyanate (a2) may be used alone or in combination of two or more. When two or more kinds are used in combination, any of the combinations of polyisocyanates having an alicyclic structure, polyisocyanates having an aromatic ring, and polyisocyanates having an alicyclic structure and polyisocyanates having an aromatic ring may be used, the combination of polyisocyanates having an alicyclic structure and polyisocyanates having an aromatic ring is preferable, and the combination of 4, 4' -dicyclohexylmethane diisocyanate (hydrogenated MDI) and a trimer adduct of trimethylolpropane and toluene diisocyanate is more preferable.
When the polyisocyanate having an alicyclic structure and the polyisocyanate having an aromatic ring are used in combination, the amount of the polyisocyanate having an alicyclic structure is preferably 1 to 40 parts by mass, more preferably 1.5 to 30 parts by mass, based on 100 parts by mass of the total amount of the polyisocyanate having an alicyclic structure and the polyisocyanate having an aromatic ring.
Since the polyisocyanate (a2) contains 2 to 6 monocyclic alicyclic structures or 3 to 7 monocyclic aromatic rings, the cured product of the curable composition has excellent electrical insulation properties and also has excellent crack resistance even in a portion where photocuring is insufficient.
The total content of the polyisocyanate having 2 to 6 monocyclic alicyclic structures or 3 to 7 monocyclic aromatic rings in one molecule in the polyisocyanate (a2) is preferably 50% by mass or more, more preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, particularly preferably 90% by mass or more, and most preferably 100% by mass. When the total content of the polyisocyanate having 2 to 6 monocyclic alicyclic structures or 3 to 7 monocyclic aromatic rings in one molecule is 50% by mass or more, a cured product of the curable composition has excellent electrical insulation properties and also has excellent crack resistance even in a portion where photocuring is insufficient.
The polyurethane resin (a) is a polymer of monomers including an alcohol (a1) and a polyisocyanate (a2), and the alcohol (a1) contains a polyol (a1-1) as an essential component. In the monomers to be the raw materials of the polyurethane resin (a), the equivalent ratio (isocyanate group/hydroxyl group) of the isocyanate group in the polyisocyanate (a2) to the hydroxyl group in the alcohol (a1) is greater than 1 and 8 or less, preferably greater than 1 and 7 or less, and more preferably greater than 1 and 6 or less. When the equivalent ratio (isocyanate group/hydroxyl group) is 8 or less, the urethane resin (a) has a molecular weight of a sufficient size, and thus a cured product of the curable composition has excellent electrical insulation properties and also has excellent crack resistance even in a portion where photocuring is insufficient. In order to impart moisture curability to the polyurethane resin (a), the equivalent ratio (isocyanate group/hydroxyl group) must be greater than 1, and the storage stability of the curable composition is improved, so that it is preferably 2 or more, more preferably 2.5 or more.
The equivalent ratio (isocyanate group/hydroxyl group) of the isocyanate group in the polyisocyanate (a2) to the hydroxyl group in the alcohol (a1) is determined by dividing the number of isocyanate groups in the polyisocyanate (a2) by the number of hydroxyl groups in the alcohol (a 1).
The number of hydroxyl groups in the alcohol (a1) was calculated based on the following formula. The hydroxyl value is a value in accordance with JIS K1557-1: 2007(ISO 14900: 2001) "Plastic-polyurethane raw Material polyol test method-part 1: hydroxyl value determination method "4.2B method and the obtained value.
Number of hydroxyl groups in alcohol (a1)
The content of the alcohol (a1) in the monomer to be used as a raw material × hydroxyl value
/56100
The number of isocyanate groups in the polyisocyanate (a2) was calculated based on the following formula. The isocyanate equivalent weight is a value obtained by dividing the number of isocyanate groups in one molecule by the molecular weight of the polyisocyanate. Specifically, the value is measured according to JIS K1603.
Number of isocyanate groups in polyisocyanate (a2)
The content of polyisocyanate (a2) in the monomer to be used as a raw material
Isocyanate equivalent weight
The weight average molecular weight of the polyurethane resin (A) is preferably 5000 to 100000, more preferably 5000 to 50000, and particularly preferably 10000 to 25000. When the weight average molecular weight of the polyurethane resin (a) is 5000 or more, the electrical insulation property and crack resistance of a cured product of the curable composition are improved. When the weight average molecular weight of the polyurethane resin (a) is 100000 or less, the curable composition has a low viscosity and the workability is improved.
The weight average molecular weight of the polyurethane resin (a) is a value obtained by converting the molecular weight measured by Gel Permeation Chromatography (GPC) into polystyrene. For example, the measurement can be performed under the following measurement conditions.
The device comprises the following steps: HLC-8220GP made by Tosoh corporation
Column: tosoh corporation
2 roots under the trade name "TSKgel SuperHZM-H
Column temperature: 40 deg.C
Eluent: tetrahydrofuran (THF)
And (3) detection: RI (Ri)
Standard curve standard polystyrene: product name of "TSKgel Standard polystyrene" manufactured by Tosoh corporation "
The content of the polyisocyanate (a2) component in the polyurethane resin (a) is preferably 1 to 99 mass%, more preferably 5 to 80 mass%, and particularly preferably 15 to 70 mass%.
The polyurethane resin (a) can be produced by a known polymerization method. Specifically, the polyurethane resin (a) can be produced by polymerizing a monomer serving as a raw material, which contains the alcohol (a1) containing the polyol (a1-1) and, if necessary, the hydroxyl group-containing (meth) acrylate (a1-2) and the polyisocyanate (a2), so that the equivalent ratio (isocyanate group/hydroxyl group) of the isocyanate group in the polyisocyanate (a2) to the hydroxyl group in the alcohol (a1) falls within the above-described range, by a known polymerization method. The polymerization of the urethane resin (a) may be carried out in a monofunctional alkyl (meth) acrylate described later.
More specifically, the urethane resin (a) can be produced by supplying the polyisocyanate (a2) in addition to the monofunctional alkyl (meth) acrylate to the reaction vessel, then simultaneously or intermittently supplying the alcohol (a1) from which moisture has been removed to the reaction vessel, and reacting the alcohol (a2) with the polyisocyanate until the hydroxyl group of the alcohol (a1) is substantially eliminated.
The polymerization of the polyurethane resin (A) is preferably carried out at 10 to 120 ℃ for 0.5 to 10 hours.
The polymerization reaction of the polyurethane resin (a) may be carried out in the presence of a urethane-forming catalyst as required. Examples of the urethane-forming catalyst include organic metal compounds such as dibutyltin oxide, tin 2-ethylhexanoate, tin octylate, and dibutyltin dilaurate.
The content of the urethane resin (a) in the curable composition is preferably 15 to 60 mass%, preferably 30 to 60 mass%, more preferably 35 to 50 mass%, and particularly preferably 40 to 48 mass% with respect to 100 mass% of the total amount of the urethane resin (a), the monofunctional alkyl (meth) acrylate (B), and the photopolymerization initiator (C). When the content of the urethane resin (a) is 15% by mass or more, a cured product of the curable composition has excellent electrical insulation properties and also has excellent crack resistance in a portion where photocuring is insufficient. When the content of the urethane resin (a) is 60% by mass or less, the viscosity of the curable composition becomes low, and the workability is improved.
[ monofunctional (meth) acrylate ]
The curable composition contains a monofunctional (meth) acrylate (B) which does not contain a ring structure and has an alkyl group having 10 or less carbon atoms. Monofunctional means that only 1 radical polymerizable unsaturated bond is present in one molecule. The alkyl group means a group of atoms remaining after removal of 1 hydrogen atom from an aliphatic saturated hydrocarbon, and its general formula is-CnH2n+1It means that it does not contain a hetero atom such as nitrogen and sulfur. The ring structure refers to all cyclic structures formed by carbon and other atoms (nitrogen, sulfur, etc.).
Since the monofunctional (meth) acrylate (B) having no ring structure and an alkyl group having 10 or less carbon atoms is contained, a cured product of the curable composition has excellent electrical insulation properties, and also has excellent crack resistance even in a portion where photocuring is insufficient, and further, the curable composition has excellent moisture curability.
The monofunctional (meth) acrylate (B) preferably contains no functional group reactive with an isocyanate group. Examples of the functional group reactive with an isocyanate group include a hydroxyl group, an amino group, a mercapto group, and a carboxyl group.
The number of carbon atoms of the alkyl group of the monofunctional (meth) acrylate (B) is 10 or less, preferably 2 to 10, more preferably 4 to 9, and particularly preferably 6 to 9. When the number of carbon atoms of the alkyl group is 10 or less, a cured product of the curable composition has excellent electrical insulation properties, and also has excellent crack resistance even in a portion where photocuring is insufficient, and further, moisture curability of the curable composition is improved. When the number of carbon atoms in the alkyl group is2 or more, odor from the curable composition can be suppressed.
Examples of the monofunctional (meth) acrylate (B) include alkyl (meth) acrylates such as alkyl (meth) acrylates including n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-butyl (meth) acrylate, and n-octyl (meth) acrylate, and alkyl (meth) acrylates are preferable, and alkyl acrylates are more preferable. Alternatively, n-octyl (meth) acrylate is preferred, and n-octyl acrylate is more preferred. The monofunctional (meth) acrylate may be used alone or in combination of two or more.
The content of the monofunctional (meth) acrylate (B) in the curable composition is preferably 30 to 70% by mass, more preferably 40 to 65% by mass, and particularly preferably 45 to 60% by mass, assuming that the total amount of the urethane resin (a), the monofunctional alkyl (meth) acrylate (B), and the photopolymerization initiator (C) is 100% by mass. When the content of the monofunctional (meth) acrylate (B) is 30% by mass or more, the photocurability of the curable composition is improved, and the cured product of the curable composition has excellent crack resistance. When the content of the monofunctional (meth) acrylate (B) is 70% by mass or less, a cured product having excellent electrical insulation properties and crack resistance even in a portion where photocuring is insufficient can be obtained.
[ polyfunctional (meth) acrylate (D) ]
The curable composition may contain a polyfunctional (meth) acrylate (D). The polyfunctional (meth) acrylate (D) improves the electrical insulation of the cured product of the curable composition. Polyfunctional means having 2 or more radical polymerizable unsaturated bonds in one molecule.
The polyfunctional (meth) acrylate (D) preferably does not contain a functional group reactive with an isocyanate group. Examples of the functional group reactive with an isocyanate group include a hydroxyl group, an amino group, a mercapto group, and a carboxyl group.
The polyfunctional (meth) acrylate (D) is not particularly limited, and examples thereof include: 1, 3-butanediol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) diacrylate and other alkylene glycol di (meth) acrylates, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate and other polyoxyalkylene glycol di (meth) acrylates, diacrylates of bisphenol A or alkylene oxide adducts of hydrogenated bisphenol A, trimethylolpropane tri (meth) acrylate, pentaerythritol tetraacrylate, ditrimethylol tetraacrylate, dipentaerythritol hexaacrylate and the like, alkylene glycol di (meth) acrylates are preferred, 1, 3-butanediol di (meth) acrylate is more preferred, and 1, 3-butanediol diacrylate is particularly preferred. The polyfunctional (meth) acrylate may be used alone or in combination of two or more.
The content of the polyfunctional (meth) acrylate (D) in the curable composition is preferably 15% by mass or less, more preferably 10% by mass or less, and particularly preferably 6.5% by mass or less, based on the total amount of the monofunctional (meth) acrylate (B) and the polyfunctional (meth) acrylate (D). When the content of the polyfunctional (meth) acrylate is 15% by mass or less, a cured product of the curable composition has excellent electrical insulation properties, and also has excellent crack resistance even in a portion where photocuring is insufficient, and further, the moisture curability of the curable composition is improved.
[ photopolymerization initiator (C) ]
The curable composition contains a photopolymerization initiator (C). The photopolymerization initiator is not particularly limited as long as it is decomposed by irradiation with active energy rays such as ultraviolet rays and electron beams to generate radicals, thereby initiating the photocuring reaction of the curable composition.
The photopolymerization initiator (C) is not particularly limited, and examples thereof include: benzoin, benzoin ethyl ether, benzophenone, acyl phosphine oxide; an alkylphenone compound such as 2, 2-dimethoxy-1, 2-diphenylethane-1-one; α -aminoalkylphenone compounds such as 2-methyl-1 [4- (methylthio) phenyl ] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, and 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -1-butanone; benzophenone compounds such as benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,4, 6-trimethylbenzophenone, 4-phenylbenzophenone, 4- (methylphenylthio) phenylphenylmethane, methyl-2-benzophenone, 1- [4- (4-benzoylphenylsulfanyl) phenyl ] -2-methyl-2- (4-methylphenylsulfonyl) 1-propanone, 4 ' -bis (dimethylamino) benzophenone, 4 ' -bis (diethylamino) benzophenone, N ' -tetramethyl-4, 4 ' -diaminobenzophenone, N ' -tetraethyl-4, 4 ' -diaminobenzophenone and 4-methoxy-4 ' -dimethylaminobenzophenone (ii) a Acylphosphine oxide compounds such as bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide and 2,4, 6-trimethylbenzoyl-diphenyl-phosphine oxide; oxyphenylacetic acid; phenylglyoxylate compounds such as methyl phenyloxalate; titanocene compounds such as bis (. eta.5-2, 4-cyclopentadien-1-yl) -bis (2, 6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium; and oxime ester compounds such as 1- [4- (phenylthio) -1, 2-octanedione-2- (O-benzoyloxime) and 1- [9- (ethyl) -6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone 1- (O-acetyloxime).
Photopolymerization initiators (C) are commercially available, for example, from BASF Japan under the trade names "Irgacure 184", "Irgacure 907", "Irgacure 819", "Irgacure TPO", "Irgacure 651", "Irgacure 369", "Irgacure 379 EG", "Irgacure MBF", "Irgacure 784", "Irgacure OXE 01" and "Irgacure OXE 02". The photopolymerization initiator (C) may be used alone or in combination of two or more.
The content of the photopolymerization initiator (C) in the curable composition is preferably 1 to 15% by mass, more preferably 2 to 8% by mass, and particularly preferably 3 to 7% by mass, when the total amount of the urethane resin (a), the monofunctional alkyl (meth) acrylate (B), and the photopolymerization initiator (C) is 100% by mass. When the content of the photopolymerization initiator (C) is 1% by mass or more, the photocurability of the curable composition is improved. When the content of the photopolymerization initiator (C) is 10% by mass or less, a cured product of the curable composition has excellent electrical insulation properties and crack resistance.
[ other Components ]
The curable composition contains the urethane resin (a), the monofunctional (meth) acrylate (B), and the photopolymerization initiator (C) as essential components, and may contain, as necessary: moisture curing catalyst (F), polymerization inhibitor, antioxidant, defoaming agent, leveling agent, silane coupling agent, metal deactivator and other additives, and solvent.
The moisture curing catalyst (F) is not particularly limited, and examples thereof include an organic metal compound and a tertiary amine compound. Examples of the organic metal compound include organic tin compounds such as dibutyltin dilaurate, organic iron compounds, organic zinc compounds, organic titanium compounds, organic aluminum compounds, organic zirconium compounds, and organic bismuth compounds. The moisture curing catalyst (F) may be used alone or in combination of two or more. The mixing ratio of the moisture curing catalyst (F) is not particularly limited, and may be suitably adjusted depending on the purpose and use. The moisture effect catalyst (F) can be used as a urethanization catalyst for the synthesis of the polyurethane resin (a).
Examples of the organotin compound include tin carboxylates such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin diacetylacetate, tin octylate, tin naphthenate, tin laurate and tin ferulate, and reactants of dibutyltin oxide and phthalic acid esters.
Examples of the organic iron compound include iron tris (acetylacetonate), iron tris (2,2,6, 6-tetramethyl-3, 5-heptanedionate), iron tris (tetrafluoroacetylacetonate), iron chloride, iron tris (2-ethylhexanoate), iron naphthenate, iron triethoxide, and iron triisopropoxide.
Examples of the organozinc compound include zinc bis (acetylacetonate), zinc bis (2,2,6, 6-tetramethyl-3, 5-heptanedionate), zinc bis (tetrafluoroacetylacetonate), zinc bis (2-ethylhexanoate), zinc naphthenate, diethoxy zinc, and diisopropoxy zinc.
Examples of the organic titanium compound include titanates such as tetrabutyl titanate and tetrapropyl titanate, and titanium chelate compounds such as titanium tetraacetylacetonate.
Examples of the organoaluminum compound include aluminum triacetylacetonate, tris (ethylacetoacetato) aluminum, and ethylaluminum acetoacetate diisopropoxide.
Examples of the organozirconium compound include zirconium chelate compounds such as zirconium tetraacetylacetonate.
Examples of the organic bismuth compound include bismuth-tris (neodecanoate), bismuth-tris (2-ethylhexanoate), and bismuth octylate.
Examples of the tertiary amine compound include trialkylamines such as triethylamine; tetraalkylalkylenediamines such as tetramethylethylenediamine and tetramethylhexanediamine; pentaalkyldialkylenetriamines such as pentamethyldiethylenetriamine; piperazines such as trimethylaminoethyl piperazine and dimethylpiperazine; n-alkylimidazoles such as 1, 2-dimethylimidazole; bis (dimethylaminoethyl) ether; triethylenediamine [ 1, 4-diazabicyclo [2,2,2] octane (DABCO) ]; n-methylmorpholine; 1, 8-diazabicyclo [5,4,0] -7-undecene (DBU), 2,4, 6-tris (dimethylaminomethyl) phenol, and the like.
Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, benzoquinone, p-tert-butylcatechol, and 2, 6-di-tert-butyl-4-methylphenol. The polymerization inhibitor may be used alone or in combination of two or more. The mixing ratio of the polymerization inhibitor is not particularly limited, and may be suitably adjusted depending on the purpose and use.
Examples of the antioxidant include a phenol-based antioxidant, a phosphorus-based antioxidant, and a sulfur-based antioxidant. The antioxidant may be used alone or in combination of two or more. The blending ratio of the antioxidant is not particularly limited, and may be appropriately adjusted depending on the purpose and the use. Phenolic antioxidants are commercially available, for example, from Adeka corporation under the trade names "ADK STAB AO-20", "ADK STAB AO-60" and "ADK STAB AO-80", and from BASF Japan under the trade names "Irganox 1010", "Irganox 1076", "Irganox 1135" and "Irganox 1520L". The phosphorus-based antioxidant is commercially available from Adeka corporation under the trade names "ADK STAB PEP-4C" and "ADK STAB 2112", and from BASF Japan under the trade name "Irgafos 168", for example. The sulfur-based antioxidant is commercially available, for example, from Adeka corporation under the trade names "ADK STAB AO-412S" and "ADK STAB AO-503", and from BASF Japan under the trade names "Irganox PS 800 FL" and "Irganox PS 802 FL".
Defoamers are commercially available, for example, from BYK Japan KK under the trade names "BYK-054", "BYK-057", "BYK-065", "BYK-066N", "BYK-067A" and "BYK-1794", and from Evonik corporation under the trade names "TEGO Airex 904W", "TEGO Airex 910", "TEGO Airex 920", "TEGO Airex 931", "TEGO Airex 945", "TEGO Foamex 833" and "TEGO Twinin 4000". The defoaming agent may be used alone or in combination of two or more. The mixing ratio of the defoaming agent is not particularly limited, and may be appropriately adjusted depending on the purpose and the use.
Examples of the leveling agent include a silicone leveling agent, an acrylic leveling agent, and a fluorine leveling agent. The leveling agent may be used alone or in combination of two or more. The blending ratio of the leveling agent is not particularly limited, and can be appropriately adjusted depending on the purpose and the use. Examples of the silicone-based leveling agent include those commercially available from BYK Japan KK under the trade names "BYK-300", "BYK-302", "BYK-307", "BYK-320", "BYK-322", "BYK-325", "BYK-330", "BYK-331", "BYK-333", "BYK-345", "BYK-370", "BYK-377", "BYK-378", "BYK-3455", "BYK-UV 3500" and "BYK-UV 3510", those commercially available from Evonik corporation under the trade names "TEGO FLOW 425", "TEGO 100", "TEGO 110" and "TEGO GLIDE 432", and those commercially available from Toray Dow Corning Co., Ltd under the trade names "Dow Corning 56 Additive" and "Dow Corning 57 Additive". Acrylic leveling agents are commercially available, for example, from BYK Japan KK under the trade names "BYK-350", "BYK-354", "BYK-356" and "BYK-3441", and from Evonik corporation under the trade names "TEGO Flow 370" and "TEGO Flow ZFS 460". As the fluorine-based leveling agent, for example, commercially available under the trade names "Novec FC-4430" and "Novec FC-4432" from Sumitomo 3M Ltd., and "Ftergent FTX-218", "Ftergent 710 FL" and "Ftergent 601 AD" from Neos Corporation.
Silane coupling agents are commercially available, for example, from Shin-Etsu Silicones corporation under the trade names "KBM-1003", "KBE-1003", "KBM-503", "KBM-5103", and "KBE-9007". The silane coupling agent may be used alone or in combination of two or more. The mixing ratio of the silane coupling agent is not particularly limited, and may be appropriately adjusted depending on the purpose and the use.
The metal deactivators are commercially available, for example, from Adeka corporation under the trade names "ADK STAB CDA-1", "ADK STAB CDA-1M", "ADK STAB CDA-6" and "ADK STAB CDA-10", from BASF Japan corporation under the trade name "Irganox MD 1024", and from North City chemical industry Co., Ltd under the trade names "BT-120", "BT-LX" and "TT-LX".
Examples of the solvent include hydrocarbons such as pentane, hexane, heptane and cyclohexane, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, and esters such as ethyl acetate and butyl acetate. The solvent may be used alone or in combination of two or more.
The curable composition can be produced by stirring and mixing the urethane resin (a), the monofunctional (meth) acrylate (B), the photopolymerization initiator (C), and other additives with a general-purpose stirrer.
The curable composition can be used, for example, as a conformal coating agent, and specifically, is used for electrically insulating an electronic circuit substrate after soldering in order to protect the electronic circuit substrate from water, moisture, dust, and the like.
Specifically, a curable composition is applied to an electronic component of an electronic circuit board formed by soldering the electronic component on a substrate, and the electronic component is covered with the curable composition.
The curable composition is irradiated with active energy rays (for example, ultraviolet rays, electron beams, or the like) to cause radical polymerization of the monofunctional (meth) acrylate and, if necessary, the polyfunctional (meth) acrylate and the hydroxyl group-containing (meth) acrylate component of the urethane resin (a), thereby photo-curing the composition. When the curing is carried out simultaneously with the photocuring and the active energy ray irradiation, the isocyanate group of the urethane resin (a) of the curable composition reacts with moisture in the air to cause a crosslinking reaction, and the moisture curing is carried out to produce a cured product.
The cured product thus produced has excellent electrical insulation properties, and also has sufficient crack resistance even in portions not irradiated with active energy rays or portions not irradiated with active energy rays, and further, the cured product has excellent appearance properties (transparency). Therefore, the cured product of the curable composition stably protects the electronic component from contaminants such as water, dust, and metal powder for a long period of time while maintaining the electronic component in an electrically insulated state. Further, since the cured product of the curable composition has excellent transparency, the state of the electronic component can be easily visualized through the cured product after covering and protection, and the maintenance of the electronic circuit board can be easily performed.
Examples
The present invention will be described in further detail with reference to examples, but the present invention is not limited to these examples.
The compounds used for preparing the curable composition are shown below. In the case where a solvent is contained in the product, the kind of the solvent and the solid content of the compound are shown.
[ polyol (a1-1) ]
Hydrogenated polybutadiene diol 1 (product name "GI-3000" manufactured by Nippon Caoda corporation), number average molecular weight: 3000. iodine value: below 21
Hydrogenated polybutadiene diol 2 (product name "GI-2000" from Nippon Caoda corporation), number average molecular weight: 2100. iodine value: below 21
Hydrogenated polyisoprene diol (Idemitsu Kosan co., trade name "EPOL" manufactured by ltd.), number average molecular weight: 2500. iodine value: 7.9
Polycarbonate diol 1 (product name "Duranol T5652" manufactured by Asahi Kasei Chemicals Company)
Polycarbonate diol 2 (product name: PLACCEL CD220PL, manufactured by Daicel Corporation)
Polyester Polyol (Kuraray Co., Ltd., product name "Kuraray Polyol P-1010")
Acrylic polyol (trade name "ARUFON UH-2000" manufactured by Toyo Synthesis Co., Ltd.)
[ polyisocyanate (a2) ]
A trimer adduct of trimethylolpropane and tolylene diisocyanate (TMP-TDI) (product name "Coronate L" manufactured by Tosoh corporation, ethyl acetate, solid content: 75 mass%), an aromatic ring: 3 are provided with
4, 4' -dicyclohexylmethane diisocyanate (hydrogenated MDI) (Sumika Covestro Urethane Co., Ltd., product name "Desmodur W" manufactured by Ltd.), alicyclic structure: 2 are provided with
Isocyanurate body of toluene diisocyanate (TDI/isocyanurate) (Sumika Covestro Urethane Co., Ltd. trade name "Desmodur IL 1451", butyl acetate, solid content: 51 mass%), aromatic ring: 3 are provided with
1, 3-bis (isocyanatomethyl) cyclohexane (hydrogenated m-XDI) (tradename of Mitsui chemical "Takenate 600"), alicyclic structure: 1 is provided with
Isocyanurate body of hexamethylene diisocyanate (HDI/isocyanurate) (trade name "Duranate MHG-80B" manufactured by Asahi Kasei Chemicals Company, butyl acetate, solid content: 80 mass%), alicyclic structure and aromatic ring: 0 number of
Hexamethylene diisocyanate prepolymer (HDI/prepolymer) (product name "Duranate D201" by Asahi Kasei Chemicals Company), alicyclic structure and aromatic ring: 0 number of
[ hydroxyl group-containing acrylate (a1-2) ]
Pentaerythritol triacrylate (PETA) (product name "Aronix M-306" manufactured by Toyo Synthesis Co., Ltd.)
[ urethane acrylate ]
Urethane acrylate (trade name "TEAI-1000" manufactured by japan caoka corporation), having a hydrogenated butadiene skeleton and a urethane bond in the main chain, having acryl groups at both ends, and having a number average molecular weight: 2000
[ polyisocyanate (E) ]
A trimer adduct of trimethylolpropane and tolylene diisocyanate (TMP-TDI) (product name "Coronate L" manufactured by tokyo corporation), an aromatic ring: 3 are provided with
A reaction product of a trimer adduct of trimethylolpropane and tolylene diisocyanate (TMP-TDI) (trade name "Coronate L" manufactured by Tosoh Corp.) and pentaerythritol triacrylate (trade name "Aronix M-306" manufactured by Toyao Kabushiki Kaisha)
[ monofunctional acrylate (B) ]
N-octyl acrylate (trade name "NOAA" manufactured by osaka organic chemical industries, ltd.), glass transition temperature: -65 deg.C
Lauryl acrylate (trade name "LA" manufactured by osaka organic chemical industry co., ltd.), glass transition temperature: -23 deg.C
Isobornyl acrylate (product name "IBXA" manufactured by osaka organic chemical industry co., ltd.), glass transition temperature: 97 deg.C
[ polyfunctional acrylate (D) ]
1, 3-butanediol diacrylate (trade name "SR 212B" manufactured by Sartomer Company), glass transition temperature: 101 deg.C
[ photopolymerization initiator (C) ]
Bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide (product name "Irgacure 819" from BASF corporation)
[ moisture curing catalyst (F), urethanization catalyst ]
Dibutyltin dilaurate (DBTDL) (trade name "TN-12" made by Sakai chemical industry Co., Ltd.)
(Synthesis examples 1 to 10, comparative Synthesis examples 1 to 11)
In a reaction vessel, predetermined amounts of polyol (a1-1), polyisocyanate (a2), hydroxyl group-containing acrylate (a1-2), monofunctional acrylate (B), polyfunctional acrylate (D) and 4-methoxyphenol (trade name "MQ" manufactured by Kaikou chemical Co., Ltd.) as a polymerization inhibitor were supplied to each of the reaction vessels shown in tables 1 to 4, and the inside of the reaction vessel was heated to 60 ℃ while bubbling dry air and stirring. The equivalent ratio of isocyanate groups in the polyisocyanate (a2) to hydroxyl groups in the alcohol (a1) (isocyanate group/hydroxyl group) is defined in the column of "equivalent ratio (isocyanate group/hydroxyl group)". The numerical values in tables 1 to 4 are all in terms of solid components other than the solvent.
When the monofunctional acrylate (B) and the polyfunctional acrylate (D) are used as reaction solvents to prepare the polyurethane resin (a), a part of the monofunctional acrylate (B) and the polyfunctional acrylate (D) blended in the curable composition is added to the reaction system.
Then, a predetermined amount of dibutyltin dilaurate as a urethane-forming catalyst shown in tables 1 to 4 was added thereto and the mixture was held for 3 hours to obtain a polyurethane resin (a). The weight average molecular weight of the obtained polyurethane resin (A) is shown in tables 1 to 4.
(Synthesis of polyisocyanate (E) used in comparative example 13)
A polyisocyanate [ a trimer adduct of trimethylolpropane and tolylene diisocyanate (TMP-TDI) ] (product name "Coronate L" manufactured by Tosoh Corp.) 59.8 parts by mass (in terms of solid content), pentaerythritol triacrylate (PETA) (product name "Aronix M-306" manufactured by Toyo chemical Co., Ltd.) 40.2 parts by mass, dibutyltin dilaurate (DBTDL)0.01 part by mass, n-octyl acrylate (product name "NOAA" manufactured by Osaka organic chemical Co., Ltd.) 80.1 parts by mass, and 4-methoxyphenol MQ (product name "MQ" manufactured by Kawakawa chemical Co., Ltd.) as a polymerization inhibitor 0.1 part by mass were mixed and dissolved with stirring, and heated at 60 ℃ for 2 hours to obtain an acryloyl group-containing polyisocyanate.
Examples 1 to 10 and comparative examples 1 to 11
The urethane resin (a), the monofunctional acrylate (B), the photopolymerization initiator (C), the polyfunctional acrylate (D), and dibutyltin dilaurate as the moisture curing catalyst (F) were supplied to a planetary mixer in the predetermined amounts shown in tables 5 to 8, and were uniformly mixed by stirring, thereby obtaining a curable composition. The polyurethane resin (a) used is described in the columns of the types of polyurethane resins (a) in tables 5 to 8.
The urethane resin (a) prepared in the above includes the monofunctional acrylate (B) or the polyfunctional acrylate (D), but the numerical values in the column of the urethane resin (a) shown in tables 5 to 8 are amounts other than the monofunctional acrylate (B) and the polyfunctional acrylate (D). The numerical values in the columns of the monofunctional acrylate (B) and the polyfunctional acrylate (D) shown in tables 5 to 8 are values each including the amount of the monofunctional acrylate (B) and the polyfunctional acrylate (D) added in the preparation of the polyurethane resin (a), and are the total amount of the monofunctional acrylate (B) and the polyfunctional acrylate (D) contained in the curable composition. The values in tables 5 to 8 are values in terms of solid components other than the solvent.
Comparative examples 12 and 13
Urethane acrylate, polyisocyanate (E), monofunctional acrylate (B), photopolymerization initiator (C), polyfunctional acrylate (D), and dibutyltin dilaurate as a moisture curing catalyst (F) were supplied to a planetary mixer in the predetermined amounts shown in table 8, and were stirred and uniformly mixed to obtain a curable composition.
The obtained curable compositions were measured for electrical insulation, crack resistance, appearance and moisture curability in the following manner, and the results are shown in tables 5 to 8.
(Electrical insulation)
A curable composition was applied to a JIS2 type comb substrate to a film thickness of 50 μm to prepare 2 test pieces. After the curable composition was photocured by irradiating the curable composition of 1 test piece with ultraviolet rays having an emission wavelength of 365nm, the test piece was left to stand in an atmosphere of 23 ℃ and a relative humidity of 50% for 12 hours to cure the curable composition with moisture, thereby producing a cured product.
The other test piece was left standing at 23 ℃ under an atmosphere of 50% relative humidity for 12 hours without being irradiated with ultraviolet rays, and the curable composition was moisture-cured to give a cured product.
After 2 test pieces were placed in a constant-humidity incubator maintained at 85 ℃ and a relative humidity of 85%, the applied voltage was set to 32V, and the resistance value of the cured product after 96 hours was measured.
The resistance value of the cured product of the test piece irradiated with ultraviolet light is shown in the column "UV part", and the resistance value of the cured product of the test piece not irradiated with ultraviolet light is shown in the column "dark part".
(crack resistance)
And coating reflow soldering flux on the glass epoxy substrate, and carrying out resistance welding on the chip. Next, a curable composition was applied to the chip resistor, and the chip resistor was covered with the curable composition to prepare 2 test pieces.
After the curable composition was photocured by irradiating the curable composition of 1 test piece with ultraviolet rays having an emission wavelength of 365nm, the test piece was left to stand in an atmosphere of 23 ℃ and a relative humidity of 50% for 12 hours to cure the curable composition with moisture, thereby producing a cured product.
The other test piece was left standing at 23 ℃ under an atmosphere of 50% relative humidity for 12 hours without being irradiated with ultraviolet rays, and the curable composition was moisture-cured to give a cured product.
After the test piece was held at 125 ℃ for 30 minutes, the test piece was held at-40 ℃ for 30 minutes, and subjected to a 1-cycle cold-heat cycle test, and the number of cycles that had been completely performed at the time when the crack started to be generated in the cured product was counted. Evaluation was carried out according to the following criteria.
The number of cycles of the test piece irradiated with ultraviolet light is shown in the column "UV part", and the number of cycles of the test piece not irradiated with ultraviolet light is shown in the column "dark part".
A + +: the number of cycles is 2000 or more.
A +: the number of cycles is 1500 or more and less than 2000.
A: the number of cycles is 1000 or more and less than 1500.
B: the number of cycles is 720 or more and less than 1000.
C: the number of cycles is 360 or more and less than 720.
D: the number of cycles is less than 360.
(appearance)
The curable composition was applied to a glass plate in a film thickness of 50 μm. The curable composition is irradiated with ultraviolet rays having an emission wavelength of 365nm to photocure the curable composition. The HAZE value (HAZE value) of a cured product of the curable composition was measured by a HAZE meter (trade name "NDH 5000", manufactured by Nippon Denshoku industries Co., Ltd.). Note that the glass plate was subtracted as a background. The smaller the HAZE value, the higher the transparency of the cured product. Evaluation was performed based on the following criteria.
A +: the HAZE value is 0 or more and less than 0.25.
A: the HAZE value is 0.25 or more and less than 0.5.
B: the HAZE value is 0.5 or more and less than 1.0.
C: the HAZE value is 1.0 or more and less than 2.0.
D: the HAZE value is 2.0 or more.
(moisture curing)
The curable composition was coated on a glass epoxy substrate to a film thickness of 50 μm, and the coated surface of the curable composition was left to stand in a dark environment at 23 ℃ under a relative humidity of 50%. At each time point 6 hours, 12 hours, and 24 hours after the completion of coating, the glass epoxy substrate was held so that the coating surface of the curable composition was vertical, whether or not sagging of the curable composition occurred was visually observed, and the evaluation was performed based on the time required for not causing sagging of the curable composition as follows.
A: less than 6 hours.
B: more than 6 hours and less than 12 hours.
C: more than 12 hours and less than 24 hours.
D: sagging occurred in the curable composition at the time of 24 hours.
[ Table 1]
[ Table 2]
[ Table 3]
[ Table 4]
[ Table 5]
[ Table 6]
[ Table 7]
[ Table 8]
Industrial applicability
The curable composition of the present invention can be suitably used for the purpose of protecting an electronic circuit board after soldering from electrical insulation treatment such as water, moisture, and dust.
(cross-reference to related applications)
The disclosure of the application, based on the priority of the japanese patent application No. 2016-.
Claims (7)
1. A curable composition characterized by comprising:
a polyurethane resin (A) having a hydrogenated butadiene-based skeleton and/or a hydrogenated isoprene-based skeleton, and is a polymer containing an alcohol (a1) and a polyisocyanate (a2) as monomer components and having an isocyanate group, the alcohol (a1) comprises a polyol (a1-1) comprising a hydrogenated polybutadiene polyol and/or a hydrogenated polyisoprene polyol, the polyurethane resin (A) is a polymer of a monomer which contains the alcohol (a1) and the polyisocyanate (a2) and has an equivalent ratio (isocyanate group/hydroxyl group) of isocyanate groups in the polyisocyanate (a2) to hydroxyl groups in the alcohol (a1) of more than 1 and 8 or less, the polyisocyanate (a2) comprises a polyisocyanate having 2 to 6 monocyclic alicyclic structures or 3 to 7 monocyclic aromatic rings in one molecule;
a monofunctional (meth) acrylate (B) having no ring structure and an alkyl group having 10 or less carbon atoms, the monofunctional (meth) acrylate (B) not containing a functional group that reacts with an isocyanate group; and the combination of (a) and (b),
a photopolymerization initiator (C).
2. The curable composition according to claim 1, wherein the alcohol (a1) further comprises a hydroxyl group-containing (meth) acrylate (a 1-2).
3. The curable composition according to claim 1 or claim 2, wherein the polyisocyanate (a2) comprises: 4, 4' -dicyclohexylmethane diisocyanate, and/or a trimer adduct of trimethylolpropane and toluene diisocyanate.
4. The curable composition according to claim 1, further comprising a polyfunctional (meth) acrylate (D), wherein the content of the polyfunctional (meth) acrylate (D) is 15% by mass or less in the total amount of the monofunctional (meth) acrylate (B) and the polyfunctional (meth) acrylate (D), and wherein the polyfunctional (meth) acrylate (D) does not contain a functional group reactive with an isocyanate group.
5. The curable composition according to claim 1, wherein the weight average molecular weight of the polyurethane resin (A) is from 5000 to 100000.
6. A conformal coating agent comprising the curable composition according to any one of claims 1 to 5.
7. A cured product of the curable composition according to any one of claims 1 to 5.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016069988A JP6697306B2 (en) | 2016-03-31 | 2016-03-31 | Photocurable composition with moisture curing, conformal coating agent and cured product |
| JP2016-069988 | 2016-03-31 | ||
| PCT/JP2017/013398 WO2017170932A1 (en) | 2016-03-31 | 2017-03-30 | Curable composition, conformal coating agent and cured product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109071695A CN109071695A (en) | 2018-12-21 |
| CN109071695B true CN109071695B (en) | 2021-03-26 |
Family
ID=59964792
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201780021562.6A Active CN109071695B (en) | 2016-03-31 | 2017-03-30 | Curable composition, shape-retaining coating agent, and cured product |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP6697306B2 (en) |
| CN (1) | CN109071695B (en) |
| WO (1) | WO2017170932A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6797420B2 (en) * | 2018-05-23 | 2020-12-09 | サンユレック株式会社 | Light moisture curable resin composition |
| JP7449068B2 (en) * | 2019-01-11 | 2024-03-13 | 日東シンコー株式会社 | curable composition |
| JP7382214B2 (en) * | 2019-01-11 | 2023-11-16 | 日東シンコー株式会社 | Curable compound, curable composition, and method for producing curable composition |
| US11773202B2 (en) | 2019-01-11 | 2023-10-03 | Nitto Shinko Corporation | Curable compound, curable composition, and method for producing curable composition |
| US20220396645A1 (en) | 2019-12-13 | 2022-12-15 | Nitto Shinko Corporation | Curable composition |
| KR102412526B1 (en) * | 2020-04-22 | 2022-06-23 | 도우성 | Light/moisture curable adhesive composition and the manufacturing method thereof |
| WO2024009957A1 (en) * | 2022-07-04 | 2024-01-11 | 積水化学工業株式会社 | Light/moisture curable resin composition, cured product, use of light/moisture curable resin composition, and end face protection method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102703019A (en) * | 2012-06-12 | 2012-10-03 | 烟台德邦科技有限公司 | Liquid optical clear adhesive with low solidification energy and preparation method thereof |
| CN104093800A (en) * | 2012-02-03 | 2014-10-08 | 昭和电工株式会社 | Photocurable translucent composition for adhesive sheet, and optical adhesive sheet |
| CN104830266A (en) * | 2014-02-06 | 2015-08-12 | 荒川化学工业株式会社 | Ultraviolet light solidified-type adhesive composition for optics and solidified layer and optical component thereof |
| WO2015190558A1 (en) * | 2014-06-11 | 2015-12-17 | 日本化薬株式会社 | Double-sided adhesive sheet for image display devices, and article |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105637001B (en) * | 2013-10-18 | 2019-10-01 | 积水化学工业株式会社 | Light moisture-curable resin combination, electronic component-use bonding agent and display element bonding agent |
| JP6270145B2 (en) * | 2014-04-30 | 2018-01-31 | 荒川化学工業株式会社 | UV curable adhesive composition for optics, the cured layer and optical member |
| JP6271375B2 (en) * | 2014-08-29 | 2018-01-31 | 日本化薬株式会社 | Polyurethane compound and resin composition containing the same |
| JP6320255B2 (en) * | 2014-09-12 | 2018-05-09 | 日本化薬株式会社 | Resin composition |
-
2016
- 2016-03-31 JP JP2016069988A patent/JP6697306B2/en active Active
-
2017
- 2017-03-30 WO PCT/JP2017/013398 patent/WO2017170932A1/en active Application Filing
- 2017-03-30 CN CN201780021562.6A patent/CN109071695B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104093800A (en) * | 2012-02-03 | 2014-10-08 | 昭和电工株式会社 | Photocurable translucent composition for adhesive sheet, and optical adhesive sheet |
| CN102703019A (en) * | 2012-06-12 | 2012-10-03 | 烟台德邦科技有限公司 | Liquid optical clear adhesive with low solidification energy and preparation method thereof |
| CN104830266A (en) * | 2014-02-06 | 2015-08-12 | 荒川化学工业株式会社 | Ultraviolet light solidified-type adhesive composition for optics and solidified layer and optical component thereof |
| WO2015190558A1 (en) * | 2014-06-11 | 2015-12-17 | 日本化薬株式会社 | Double-sided adhesive sheet for image display devices, and article |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6697306B2 (en) | 2020-05-20 |
| WO2017170932A1 (en) | 2017-10-05 |
| JP2017179171A (en) | 2017-10-05 |
| CN109071695A (en) | 2018-12-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109071695B (en) | Curable composition, shape-retaining coating agent, and cured product | |
| KR101393467B1 (en) | Polymerizable compound and curable composition containing same | |
| JP6381474B2 (en) | Curable polyurethane resin composition and cured product | |
| KR20140107508A (en) | Urethane (meth)acrylate and moisture-proof insulating coating material | |
| JP2010248455A (en) | Thiol group-containing adhesive resin composition | |
| TW201331247A (en) | Active energy ray curable composition for interlayer filling | |
| JP2014201593A (en) | Moisture-/light-curable composition, and electronic circuit device including cured film formed from the composition | |
| JP2008291114A (en) | Photosetting resin composition, photosetting and moistureproof insulating paint for mounted circuit board, electronic component and method for manufacturing the component | |
| CN112041360A (en) | Photocurable resin composition and adhesive using same | |
| WO2020054582A1 (en) | Urethane (meth)acrylate, active energy ray-curable composition containing same, and cured product of said composition | |
| JP6899225B2 (en) | Active energy ray-curable composition | |
| TW201446844A (en) | Resin film and method for producing same | |
| KR102418173B1 (en) | Curable resin composition for interlayer filling | |
| WO2021117804A1 (en) | Curable composition | |
| WO2022019256A1 (en) | Curable compound, curable composition, and method for producing curable composition | |
| WO2021251404A1 (en) | Curable composition | |
| WO2020145328A1 (en) | Curable composition | |
| JP7449068B2 (en) | curable composition | |
| CN113272345A (en) | Curable compound, curable composition, and method for producing curable composition | |
| JP2020132783A (en) | Urethane (meth)acrylate, active energy ray-curable composition comprising the same and its cured product | |
| JP2006045341A (en) | Photocurable resin composition, photocurable moist-proof insulating paint for mounted circuit board, insulated electronic component and its manufacturing method | |
| JP2018080273A (en) | Active energy ray-curable resin composition and method for producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |