WO2017170706A1 - 光硬化性樹脂、混合物及び光硬化性樹脂組成物 - Google Patents
光硬化性樹脂、混合物及び光硬化性樹脂組成物 Download PDFInfo
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- WO2017170706A1 WO2017170706A1 PCT/JP2017/012928 JP2017012928W WO2017170706A1 WO 2017170706 A1 WO2017170706 A1 WO 2017170706A1 JP 2017012928 W JP2017012928 W JP 2017012928W WO 2017170706 A1 WO2017170706 A1 WO 2017170706A1
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- photocurable resin
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- 239000011347 resin Substances 0.000 title claims abstract description 162
- 229920005989 resin Polymers 0.000 title claims abstract description 162
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- 239000011342 resin composition Substances 0.000 title claims abstract description 12
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims abstract description 70
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 60
- 229930195734 saturated hydrocarbon Natural products 0.000 claims abstract description 57
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 45
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims abstract description 26
- 125000003277 amino group Chemical group 0.000 claims abstract description 17
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 17
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- -1 —CH═NH Chemical group 0.000 claims description 48
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 41
- 238000009835 boiling Methods 0.000 claims description 17
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- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 11
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- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 21
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- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- ROWKJAVDOGWPAT-UHFFFAOYSA-N Acetoin Chemical compound CC(O)C(C)=O ROWKJAVDOGWPAT-UHFFFAOYSA-N 0.000 description 2
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 125000005641 methacryl group Chemical group 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 description 1
- LUCXVPAZUDVVBT-UHFFFAOYSA-N methyl-[3-(2-methylphenoxy)-3-phenylpropyl]azanium;chloride Chemical compound Cl.C=1C=CC=CC=1C(CCNC)OC1=CC=CC=C1C LUCXVPAZUDVVBT-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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
- 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
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/69—Polymers of conjugated dienes
-
- 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
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- 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
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- 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
Definitions
- the present invention relates to a photocurable resin, a mixture, and a photocurable resin composition.
- compositions containing photocurable resins have been used as protective films or adhesive sheets for various substrates.
- the isocyanate group in the isocyanate group-containing compound [a], which is a reaction product of the polyol (a1) and the polyisocyanate (a2) is a hydroxyl group of the hydroxyl group-containing (meth) acrylate (a3) and Active energy ray curing comprising a hydroxyl group of a saturated alcohol (a4), a polyisocyanate derivative [A] each forming a urethane bond, and an ethylenically unsaturated monomer [B] Type
- mold adhesive composition is disclosed and hydrogenated polybutadiene polyol etc. are described as a polyol (a1).
- the present inventors prepared and evaluated a photocurable resin using hydrogenated polybutadiene polyol or the like with reference to Patent Document 1, and the composition containing such a photocurable resin was In some cases, the adhesion after the durability test was lowered. Then, this invention aims at providing the photocurable resin excellent in adhesiveness. Another object of the present invention is to provide a mixture and a photocurable resin composition.
- the present inventors have a main chain skeleton having a repeating unit of a predetermined structure, a (meth) acryloyl group and a predetermined non-photoreactive group at the end,
- the present invention finds that a desired effect can be obtained by a photocurable resin in which the content of a specific repeating unit, the content of a (meth) acryloyl group, and the content of a non-photoreactive group are each in a predetermined range. It came to.
- the present invention is based on the above knowledge and the like, and specifically, solves the above problems by the following configuration.
- the main chain skeleton has a repeating unit represented by the following formulas (Ia) and (Ib), has a (meth) acryloyl group and a non-photoreactive group at the terminal,
- the non-photoreactive group is at least one selected from the group consisting of a saturated hydrocarbon group and an aromatic hydrocarbon group, which may have a hetero atom, No hydroxy group, amino group, —CH ⁇ NH, carboxy group or mercapto group is bonded to the end of the non-photoreactive group,
- the content of the repeating unit represented by the formula (Ia) is an amount exceeding 15 mol% of the repeating unit constituting the main chain skeleton,
- the content of the (meth) acryloyl group is 5 mol% or more of the terminal,
- the photocurable resin whose content of the said non-photoreactive group is 5 mol% or more of the said terminal.
- the double line between the broken line and the solid line represents a single bond or a double bond.
- the non-photoreactive group is a saturated hydrocarbon group which may have an ether bond.
- the non-photoreactive group is a monofunctional alcohol, A saturated hydrocarbon compound having one hydroxy group and having a heteroatom, and Formed by at least one hydroxy compound selected from the group consisting of aromatic hydrocarbon compounds having one hydroxy group and optionally having a hetero atom; 3.
- the main chain skeleton has a repeating unit represented by the following formula (IIa) and formula (IIb), has a (meth) acryloyl group and a non-photoreactive group at the terminal,
- the non-photoreactive group is at least one selected from the group consisting of a saturated hydrocarbon group and an aromatic hydrocarbon group, which may have a hetero atom, No hydroxy group, amino group, —CH ⁇ NH, carboxy group or mercapto group is bonded to the end of the non-photoreactive group,
- the content of the repeating unit represented by the formula (IIa) is 15 mol% or less of the repeating unit constituting the main chain skeleton,
- the content of the (meth) acryloyl group is 5 mol% or more of the terminal,
- the mixture containing the photocurable resin B whose content of the said non-photoreactive group is 5 mol% or more of the said terminal.
- the double line between the broken line and the solid line represents a single bond or a double bond. 6). 5.
- a photocurable resin composition comprising the photocurable resin according to any one of the above 1 to 4, a monofunctional (meth) acrylate, a photopolymerization initiator, and a plasticizer. 7).
- the photo-curing resin B contains a photocurable resin B,
- the photo-curing resin B has a repeating unit represented by the following formula (IIa) and formula (IIb) in the main chain skeleton, has a (meth) acryloyl group and a non-photoreactive group at the terminal,
- the non-photoreactive group is at least one selected from the group consisting of a saturated hydrocarbon group and an aromatic hydrocarbon group, which may have a hetero atom, No hydroxy group, amino group, —CH ⁇ NH, carboxy group or mercapto group is bonded to the end of the non-photoreactive group
- the content of the repeating unit represented by the formula (IIa) is 15 mol% or less of the repeating unit constituting the main chain skeleton,
- the content of the (meth) acryloyl group is 5 mol% or more of the terminal, 7.
- the photocurable resin composition according to 6 above wherein the content of the non-photoreactive group is 5 mol% or more of the terminal.
- the double line between the broken line and the solid line represents a single bond or a double bond.
- the photocurable resin of this invention is excellent in adhesiveness. Moreover, this invention can provide the mixture and photocurable resin composition which are excellent in adhesiveness.
- (meth) acrylate represents acrylate or methacrylate
- (meth) acryloyl represents acryloyl or methacryloyl
- (meth) acryl represents acryl or methacryl.
- a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
- each component can be used alone or in combination of two or more of the substances corresponding to the component.
- the content of the component means the total content of the two or more types of substances.
- the photocurable resin of the present invention (resin of the present invention)
- the main chain skeleton has a repeating unit represented by the following formulas (Ia) and (Ib), has a (meth) acryloyl group and a non-photoreactive group at the terminal,
- the non-photoreactive group is at least one selected from the group consisting of a saturated hydrocarbon group and an aromatic hydrocarbon group, which may have a hetero atom, No hydroxy group, amino group, —CH ⁇ NH, carboxy group or mercapto group is bonded to the end of the non-photoreactive group
- the content of the repeating unit represented by the formula (Ia) is an amount exceeding 15 mol% of the repeating unit constituting the main chain skeleton,
- the content of the (meth) acryloyl group is 5 mol% or more of the terminal, It is photocurable resin whose content of the said non-photoreactive group is 5 mol% or more of the said terminal.
- the resin of the present invention Since the resin of the present invention has such a configuration, it is considered that a desired effect can be obtained. The reason is not clear, but it is presumed that it is as follows.
- the resin of the present invention contains many repeating units represented by the above formula (Ia) and has high crystallinity. Therefore, it is considered that the resin of the present invention is hardly affected by external influences such as high temperature or high humidity. For this reason, it is speculated that high adhesiveness can be maintained even after the endurance test depending on the content of the repeating unit represented by the formula (Ia) within a predetermined range.
- the resin of this invention can provide a softness
- the main chain skeleton of the resin of the present invention has repeating units represented by the following formulas (Ia) and (Ib).
- formula (Ia) or formula (Ib) the double line between the broken line and the solid line represents a single bond or a double bond.
- the content of the repeating unit represented by the formula (Ia) is an amount exceeding 15 mol% of the repeating unit constituting the main chain skeleton of the resin of the present invention.
- the content of the repeating unit represented by the formula (Ia) is preferably 40 mol% or less of the repeating unit constituting the main chain skeleton of the resin, from the viewpoint of excellent adhesiveness and weather resistance, and preferably 25 to 35 mol. % Is more preferable.
- the microstructure of the main chain skeleton reflects the microstructure of the main chain skeleton raw polymer (for example, (hydrogenated) polybutadiene having a functional group at the terminal).
- the microstructure of the main chain skeleton raw polymer (unhydrogenated) (for example, polybutadiene having a functional group at the terminal) can be calculated by infrared absorption spectrum analysis. Specifically, the peak position derived from the microstructure (cis: 740cm -1, vinyl: 910cm -1, trans: 967cm -1) from the absorption intensity ratio of can be calculated micro structure of the main chain skeleton.
- the microstructure of the main chain skeleton raw material polymer (hydrogenated product) (eg, hydrogenated polybutadiene having a functional group at the terminal) is the same as that of the polymer used as the raw material for hydrogenation (eg, polybutadiene having a functional group at the terminal). It can be the same as the microstructure.
- the resin of the present invention has a (meth) acryloyl group and a non-photoreactive group at the end,
- the non-photoreactive group is at least one selected from the group consisting of a saturated hydrocarbon group and an aromatic hydrocarbon group, which may have a hetero atom. However, a hydroxy group, an amino group, —CH ⁇ NH, a carboxy group, or a mercapto group is not bonded to the end of the non-photoreactive group.
- the non-photoreactive group means a group that does not react with light.
- the photoreactive group means a group that reacts with light.
- the photoreactive group examples include a group having an ethylenically unsaturated bond such as a (meth) acryloyl group, a (meth) acryloyloxy group, and a vinyl group.
- the terminal means the main chain skeleton or the terminal of the resin of the present invention. Further, the terminal does not include the ethyl group or vinyl group in the above formula (Ib).
- the resin of the present invention can have a plurality of terminals.
- One preferred embodiment of the resin of the present invention is to have two terminals.
- One preferred embodiment is having a (meth) acryloyl group or a non-photoreactive group at one end.
- the edge part of a non-photoreactive group is synonymous with the terminal of the resin of this invention.
- the (meth) acryloyl group or the non-photoreactive group can be bonded to the end of the main chain skeleton directly or through an organic group.
- the organic group is not particularly limited. Examples of the organic group include a urethane bond, an ester bond, and a hydrocarbon group.
- One preferred embodiment of the organic group is that it has a hydrocarbon group bonded to at least one selected from the group consisting of a urethane bond and an ester bond.
- the hydrocarbon group is not particularly limited.
- the hydrocarbon group may have an unsaturated bond.
- the hydrocarbon group may be divalent or higher.
- Examples of the hydrocarbon group include a saturated hydrocarbon group, an aromatic hydrocarbon group, and a combination thereof.
- the saturated hydrocarbon group may be linear, branched or cyclic.
- the resin of the present invention has photocurability (photoreactivity) by having a (meth) acryloyl group.
- the (meth) acryloyl group includes a (meth) acryloyloxy group.
- the non-photoreactive group is at least selected from the group consisting of a saturated hydrocarbon group (including linear, branched or cyclic) and an aromatic hydrocarbon group, which may have a hetero atom.
- a saturated hydrocarbon group including linear, branched or cyclic
- an aromatic hydrocarbon group which may have a hetero atom.
- a hydroxy group, an amino group, —CH ⁇ NH, a carboxy group, or a mercapto group is not bonded to the end of the non-photoreactive group. It can be assumed that a hydroxy group, an amino group, —CH ⁇ NH, a carboxy group or a mercapto group is not bonded to the entire non-photoreactive group.
- the non-photoreactive group may be at least one selected from the group consisting of a saturated hydrocarbon group and an aromatic hydrocarbon group having no hetero atom.
- the non-photoreactive group is at least one selected from the group consisting of an unsubstituted saturated hydrocarbon group and an aromatic hydrocarbon group.
- the non-photoreactive group is at least one selected from the group consisting of a saturated hydrocarbon group and an aromatic hydrocarbon group having a hetero atom
- the cured product obtained after curing may be further given flexibility. it can.
- the hetero atom is not particularly limited.
- an oxygen atom, a nitrogen atom, and a sulfur atom are mentioned.
- the non-photoreactive group is at least one selected from the group consisting of a saturated hydrocarbon group and an aromatic hydrocarbon group having a hetero atom
- the saturated hydrocarbon group and the aromatic hydrocarbon group have any 1 or a plurality of carbon atoms (excluding the carbon atom at the terminal of the saturated hydrocarbon group as a non-photoreactive group) can be substituted with one or more of the above heteroatoms.
- the non-photoreactive group has a saturated hydrocarbon group having a hetero atom, and any carbon atom (excluding the carbon atom at the terminal of the saturated hydrocarbon group) possessed by the saturated hydrocarbon group is replaced with the hetero atom.
- the end portion of the resin more to the terminal side than the heteroatom is an unsubstituted alkyl group. It is preferably (linear, branched, cyclic, or a combination thereof).
- the heteroatom is bonded to at least two carbon atoms constituting the saturated hydrocarbon group or the aromatic hydrocarbon group.
- the hetero atom is, for example, an ether bond, a tertiary amine bond (three carbon atoms are bonded to one nitrogen atom), a thioether bond, a carbonyl in the saturated hydrocarbon group or the aromatic hydrocarbon group. Bonds, ester bonds, and urethane bonds can be formed.
- the non-photoreactive group may have at least one selected from the group consisting of an ether bond, a tertiary amine bond, a thioether bond, a carbonyl bond, an ester bond, and a urethane bond, for example.
- the non-photoreactive group has a hetero atom
- the non-photoreactive group has an ether bond, a tertiary amine bond, a thioether bond, from the viewpoint of improved flexibility, excellent adhesion, and excellent weather resistance.
- a saturated hydrocarbon group that may have at least one selected from the group consisting of a carbonyl bond, an ester bond, and a urethane bond is preferable, and a saturated hydrocarbon group that may have an ether bond is more preferable.
- a saturated hydrocarbon group (when the saturated hydrocarbon group has a hetero atom, the following “carbon number” means the total number of the hetero atom and the carbon number) is improved in flexibility and excellent in adhesion, weather resistance From the standpoint of superiority, the number of carbon atoms is preferably 4 or more.
- the saturated hydrocarbon group preferably has 30 or less carbon atoms, and more preferably 4 to 20 carbon atoms from the viewpoint of improving flexibility, excellent adhesion, and excellent weather resistance.
- Examples of the saturated hydrocarbon group include butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, and decyl group.
- the saturated hydrocarbon group may be linear, branched or cyclic.
- any carbon atom may be substituted with a hetero atom.
- the branched saturated hydrocarbon group include an ethylhexyl group and an isostearyl group.
- Arbitrary carbon atoms may be substituted with a hetero atom in the branched saturated hydrocarbon group.
- the saturated hydrocarbon group having a hetero atom include an alkoxyalkyl group such as butoxyethyl group and butoxypropyl group; a polyoxyalkylene group whose end is blocked with an alkyl group such as ethoxyethoxyethyl group. Can be mentioned.
- aromatic hydrocarbon group examples include a phenyl group.
- Examples of the combination of the saturated hydrocarbon group and the aromatic hydrocarbon group include a tolyl group. In the above combinations, any carbon atom may be substituted with a heteroatom.
- Examples of combinations of saturated hydrocarbon groups and aromatic hydrocarbon groups having heteroatoms include, for example, alkoxyphenyl groups such as methoxyphenyl groups; blocked with aromatic hydrocarbon groups such as 2-phenoxyethyl groups An oxyalkylene group; a polyoxyalkylene group blocked with an aromatic hydrocarbon group such as a 2- (2-phenoxyethoxy) ethyl group.
- the non-photoreactive group is composed of a saturated hydrocarbon having 4 or more carbon atoms, it is considered that the flexibility is improved and the adhesiveness is excellent.
- the non-photoreactive group is a monofunctional alcohol (an aliphatic hydrocarbon compound having one hydroxy group (saturated hydrocarbon compound)), A saturated hydrocarbon compound having one hydroxy group and having a hetero atom (other than the oxygen atom constituting the one hydroxy group; the same shall apply hereinafter), and At least one selected from the group consisting of aromatic hydrocarbon compounds, which has one hydroxy group and may have a hetero atom (other than the oxygen atom constituting the one hydroxy group; the same shall apply hereinafter) It can be formed by a hydroxy compound. However, an end portion of the saturated hydrocarbon compound or the aromatic hydrocarbon compound (the end portion is different from one hydroxy group in the monofunctional alcohol, the saturated hydrocarbon compound, or the aromatic hydrocarbon compound.
- the heteroatom does not form a hydroxy group, an amino group, —CH ⁇ NH, a carboxy group or a mercapto group.
- the 1 The resin of the present invention does not have a hydroxy group derived from one hydroxy group. Further, the hydroxy group derived from the one hydroxy group does not become a hydroxy group bonded to the end of the non-photoreactive group.
- the boiling point of the hydroxy compound is preferably 100 ° C. or higher, more preferably 100 to 350 ° C., still more preferably 100 to 250 ° C.
- the non-photoreactive group is formed by a hydroxy compound having a boiling point of 100 ° C. or higher
- the hydroxy compound is less likely to volatilize, the hydroxy compound can sufficiently react with the isocyanate group, and the residual isocyanate is reduced. Therefore, it is difficult to discolor and is considered to be excellent in weather resistance.
- a non-photoreactive group is formed with the monofunctional alcohol whose boiling point is 100 degreeC or more.
- the non-photoreactive group is formed by a monofunctional alcohol having a boiling point of 100 ° C. or higher, when the resin of the present invention is produced, the monofunctional alcohol is not easily volatilized, and the monofunctional alcohol can sufficiently react with the isocyanate group, and the residual isocyanate Therefore, it is considered difficult to discolor and excellent in weather resistance.
- the monofunctional alcohol is an aliphatic hydrocarbon compound (saturated hydrocarbon compound) having one hydroxy group.
- the aliphatic hydrocarbon group which the said monofunctional alcohol has is synonymous with the saturated hydrocarbon group which a non-photoreactive group may have.
- the boiling point of the monofunctional alcohol is preferably 100 to 350 ° C, more preferably 100 to 250 ° C. Examples of the monofunctional alcohol having a boiling point of 100 ° C. or higher include butanol, pentanol, hexanol, heptanol, octanol, ethylhexanol, and decanol.
- the hetero atom that the saturated hydrocarbon compound has has the same meaning as the hetero atom that the non-photoreactive group may have.
- the saturated hydrocarbon group which the said saturated hydrocarbon compound has is synonymous with the saturated hydrocarbon group which the said non-photoreactive group may have.
- Examples of the saturated hydrocarbon compound having a boiling point of 100 ° C. or more, having one hydroxy group, and having a hetero atom include alcoholene glycol monoalkyl ethers such as ethylene glycol monobutyl ether and butoxypropanol; Examples include polyalkylene glycol monoalkyl ethers such as diethylene glycol monoethyl ether.
- the hetero atom that the aromatic hydrocarbon compound may have has the non-photoreactive group. It is synonymous with the hetero atom which may be.
- the aromatic hydrocarbon group contained in the aromatic hydrocarbon compound has the same meaning as the aromatic hydrocarbon group that the non-photoreactive group may have.
- the content of the (meth) acryloyl group is 5 mol% or more of the terminal.
- the said terminal means the total amount of the terminal which 1 molecule of resin of this invention has, or the total amount of the terminal in the whole resin of this invention (hereinafter the same).
- the content of the (meth) acryloyl group is preferably from 10 to 95 mol%, more preferably from 40 to 90 mol%, from the viewpoint of excellent adhesion and excellent weather resistance.
- the content of the (meth) acryloyl group with respect to the terminal of the main chain skeleton (or the terminal of the resin of the present invention) is the compound used to introduce the (meth) acryloyl group to the terminal of the main chain skeleton.
- a compound for introducing a (meth) acryloyl group to the total amount of the compound used to introduce a (meth) acryloyl group and a compound used to introduce a non-photoreactive group The molar ratio of
- the content of the non-photoreactive group is 5 mol% or more of the terminal.
- the content of the non-photoreactive group is preferably 5 to 90 mol%, more preferably 10 to 60 mol%, from the viewpoint of excellent adhesion and excellent weather resistance.
- the content of the non-photoreactive group with respect to the terminal of the main chain skeleton is the compound used to introduce the non-photoreactive group with respect to the terminal of the main chain skeleton. Used to introduce non-photoreactive groups relative to the molar ratio of the compound or the total amount of compounds used to introduce (meth) acryloyl groups and non-photoreactive groups The molar ratio of the resulting compounds.
- R 1 each independently represent a backbone skeleton
- R 2 each independently represents an organic group
- R 3 represents an organic group having a (meth) acryloyl group
- R 4 is a non-photoreactive
- m is 1 to 9
- n is 1 to 9
- k is 0 or 1 to 10.
- the main chain skeleton, the organic group, the (meth) acryloyl group, the organic group bonded to the (meth) acryloyl group, and the non-photoreactive group are the same as described above.
- the main chain skeleton has a repeating unit represented by the above formulas (Ia) and (Ib), has a functional group (for example, a hydroxy group) at the terminal, and has a repeating unit represented by the formula (Ia).
- Polyisocyanate is mixed with functional group-terminated polybutadiene or functional group-terminated hydrogenated polybutadiene (for example, hydroxyl-terminated polybutadiene or hydroxyl-terminated hydrogenated polybutadiene) whose content exceeds 15 mol% of the repeating units constituting the main chain skeleton.
- urethane prepolymer having an isocyanate group at the terminal is obtained, and a compound having a hydroxy group and a (meth) acryloyl group and the hydroxy compound (for example, a monofunctional alcohol) are added to the urethane prepolymer.
- a photocurable resin can be produced by the reaction.
- the main chain skeleton has a repeating unit represented by the above formula (Ia) and formula (Ib), has a functional group (for example, a hydroxy group) at the terminal, Functional group-terminated polybutadiene or functional group-terminated hydrogenated polybutadiene (for example, hydroxyl-terminated polybutadiene or hydroxyl-terminated hydrogenated) in which the content of the repeating unit represented by Ia) exceeds 15 mol% of the repeating units constituting the main chain skeleton Polybutadiene) is mixed with polyisocyanate and reacted to obtain a urethane polymer having a hydroxyl group at the terminal, and a compound having polyisocyanate, hydroxy group and (meth) acrylate in advance, and the above hydroxy compound (for example, monofunctional alcohol) (The NCO / OH (molar ratio) during the reaction is preferably 2/1).
- a functional group for example, a hydroxy group
- a compound obtained by reacting the urethane prepolymer with a compound having a polyisocyanate and a hydroxy group and (meth) acrylate (NCO / OH (molar ratio) in the reaction is preferably 2/1
- a compound obtained by reacting a polyisocyanate with the hydroxy compound (for example, a monofunctional alcohol) (NCO / OH (molar ratio) in the reaction is preferably 2/1) can be added.
- Each raw material used when manufacturing the resin of the present invention is not particularly limited except the above-mentioned provisions. It can select suitably according to the structure of resin of this invention. The amount of the raw material used can be appropriately selected so as to obtain the target compound.
- the resin of the present invention may contain resins having different contents of (meth) acryloyl groups or non-photoreactive groups.
- Examples of the functional group possessed by the functional group-terminated polybutadiene or the functional group-terminated hydrogenated polybutadiene used in the two production methods include a hydroxy group, an amino group, a carboxy group, and a mercapto group.
- the functional group-terminated polybutadiene or the functional group-terminated hydrogenated polybutadiene may be mentioned as one of preferred embodiments having functional groups at at least two terminals, respectively.
- the functional groups may be of the same type or different types.
- the polyisocyanate used in the method for producing a resin of the present invention is not particularly limited as long as it is a compound having a plurality of isocyanate groups.
- tolylene diisocyanate TDI
- diphenylmethane diisocyanate 1,4-phenylene diisocyanate
- polymethylene polyphenylene polyisocyanate xylylene diisocyanate (XDI)
- TMXDI tetramethylxylylene diisocyanate
- TODI tolidine diisocyanate
- Aromatic polyisocyanates such as naphthalene diisocyanate (NDI), triphenylmethane triisocyanate; hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate (NBDI), transcyclohexane-1,4 -Diisocyan
- the hydroxy compound used when producing the resin of the present invention is the same as the hydroxy compound capable of forming the non-photoreactive group.
- the compound having a hydroxy group and a (meth) acryloyl group used in the method for producing a resin of the present invention include a compound having one hydroxy group and a (meth) acryloyl group.
- the hydroxy group and the (meth) acryloyl group can be bonded to an organic group.
- the organic group is not particularly limited.
- Examples of the compound include hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate and hydroxybutyl (meth) acrylate.
- the mixture of the present invention comprises: A photocurable resin of the present invention;
- the main chain skeleton has a repeating unit represented by the following formula (IIa) and formula (IIb), has a (meth) acryloyl group and a non-photoreactive group at the terminal,
- the non-photoreactive group is at least one selected from the group consisting of a saturated hydrocarbon group and an aromatic hydrocarbon group, which may have a hetero atom, No hydroxy group, amino group, —CH ⁇ NH, carboxy group or mercapto group is bonded to the end of the non-photoreactive group,
- the content of the repeating unit represented by the formula (IIa) is 15 mol% or less of the repeating unit constituting the main chain skeleton,
- the content of the (meth) acryloyl group is 5 mol% or more of the terminal, It is a mixture containing the photocurable resin B whose content of the non-photoreactive group is 5 mol% or more of the
- the photocurable resin contained in the mixture of the present invention is not particularly limited as long as it is the photocurable resin of the present invention.
- the photocurable resin of the present invention is also referred to as a photocurable resin A.
- the photocurable resin B contained in the mixture of the present invention is photocurable except that the content of the repeating unit represented by the formula (IIa) is 15 mol% or less of the repeating unit constituting the main chain skeleton. It can be the same as the resin A.
- the structure of formula (IIa) is the same as that of formula (Ia), and the structure of formula (IIb) is the same as that of formula (Ib).
- the content of the repeating unit represented by the formula (IIa) is preferably 15 mol% or less, preferably 1 to 15 mol% of the repeating unit constituting the main chain skeleton, from the viewpoint of excellent adhesion and excellent weather resistance. More preferred.
- the content of the repeating unit represented by the formula (IIb) is preferably 85 mol% or more of the repeating unit constituting the main chain skeleton from the viewpoint of excellent adhesion and excellent weather resistance, and 85 to 99 mol% is preferable. More preferred.
- the content of the photocurable resin B is preferably 30% by mass or less, more preferably 1 to 30% by mass with respect to the content of the photocurable resin A, from the viewpoint that the adhesiveness is excellent and the weather resistance is excellent. .
- the production method of the mixture of the present invention is not particularly limited.
- the mixture of the present invention can be produced in the same manner as the
- the photocurable resin composition of the present invention (the composition of the present invention) is a photocurable resin comprising the photocurable resin of the present invention, a monofunctional (meth) acrylate, a photopolymerization initiator, and a plasticizer. It is a resin composition.
- the photocurable resin contained in the composition of the present invention is not particularly limited as long as it is the photocurable resin (photocurable resin A) of the present invention.
- the monofunctional (meth) acrylate contained in the composition of the present invention is not particularly limited as long as it is a compound having one (meth) acryloyloxy group.
- the (meth) acryloyloxy group can be bonded to an organic group.
- the organic group is not particularly limited.
- monofunctional (meth) acrylates include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and carbitol (meth) acrylate.
- the monofunctional (meth) acrylate is at least one selected from the group consisting of an alicyclic hydrocarbon group and a chain hydrocarbon group, which may have an unsaturated bond, because of superior adhesion and weather resistance.
- a compound having a seed is preferable, and at least one selected from the group consisting of dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate and isodecyl (meth) acrylate is more preferable.
- the content of the monofunctional (meth) acrylate is 100 parts by mass of the photocurable resin A and the photocurable resin B when the composition of the present invention further contains the photocurable resin B. 5 to 50 parts by mass is preferable, and 10 to 30 parts by mass is more preferable, based on parts (hereinafter collectively referred to as 100 parts by mass of the photocurable resin A and the like).
- Photopolymerization initiator examples include carbonyl compounds such as alkylphenone compounds, benzoin ether compounds, and benzophenone compounds, sulfur compounds, azo compounds, peroxide compounds, phosphine oxide compounds, and the like.
- acetophenone benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, acetoin, butyroin, toluoin, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, ⁇ , ⁇ -dimethoxy- ⁇ -Phenylacetophenone, methylphenylglyoxylate, ethylphenylglyoxylate, 4,4'-bis (dimethylaminobenzophenone), 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenyl Carbonyl compounds such as ketones; sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide; azobisisobutyronitrile, azobis-2,4 Azo compounds such as valeronitrile; benzoyl peroxid
- 1-hydroxycyclohexyl phenyl ketone 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2- Methyl-1-propan-1-one is preferred.
- Examples of commercially available 1-hydroxycyclohexyl phenyl ketone include Irgacure 184 (manufactured by Ciba Specialty Chemicals).
- the content of the photopolymerization initiator is preferably 1 to 10 parts by mass and more preferably 2 to 8 parts by mass with respect to 100 parts by mass of the photocurable resin A and the like.
- the plasticizer contained in the composition of the present invention is not particularly limited.
- one that is liquid at room temperature is one preferred embodiment.
- Specific examples of the compound include esters of polyoxyalkylene polyols such as polyethylene glycol di2-ethylhexate; polyolefins such as polyethylene wax.
- the content of the plasticizer is preferably 5 to 100 parts by mass and more preferably 10 to 30 parts by mass with respect to 100 parts by mass of the photocurable resin A and the like.
- the composition of the present invention may further contain a photocurable resin B.
- the photocurable resin B that can be further contained in the composition of the present invention is the same as the photocurable resin B contained in the mixture of the present invention.
- composition of the present invention can further contain an additive as long as the object of the present invention is not impaired.
- additives include polymers other than the photocurable resins A and B, fillers, anti-aging agents, antioxidants, antistatic agents, flame retardants, adhesion imparting agents, leveling agents, dispersants, and antifoaming agents. , Matting agents, light stabilizers (such as hindered amine compounds), dyes, pigments, and the like.
- composition of the present invention is not particularly limited with respect to its production method.
- the composition of the present invention can be produced by, for example, a method of mixing each of the above essential components and optional components using a stirrer such as a mixing mixer under reduced pressure.
- the composition of the present invention can be cured by light, for example.
- the light with which the composition of the present invention is irradiated is not particularly limited.
- An example is ultraviolet light.
- the wavelength of the light can be 200 to 400 nm.
- the amount of light can be 100 to 300 mW / cm 2 and the integrated amount of light can be 1000 to 3000 mJ / cm 2 .
- the apparatus used for irradiating light is not particularly limited.
- the temperature conditions for curing the composition of the present invention are not particularly limited. For example, the temperature can be 0 to 150 ° C.
- the composition of the present invention can be used as, for example, an adhesive or a coating material.
- the substrate (adhered body) to which the composition of the present invention can be applied is not particularly limited. Examples thereof include glass, plastic, rubber, and metal.
- the composition of the present invention can be, for example, an optical transparent resin (OCR: Optical Clear Resin).
- OCR optical Clear Resin
- the OCR can be bonded to a cover glass of a touch panel, a transparent conductive member, a liquid crystal module, or the like.
- HLBH-P2000 (manufactured by Clay Valley Co., Ltd., the same shall apply hereinafter) 12.9 parts by mass of isophorone diisocyanate (manufactured by Evonik, the same shall apply hereinafter) is mixed with 100 parts by mass and reacted at 70 ° C. for 5 hours under a nitrogen atmosphere. A urethane prepolymer having an isocyanate group at the terminal was obtained.
- Photocurable resin A-1 has a main chain skeleton having repeating units represented by the above formulas (Ia) and (Ib), and is a double line consisting of a broken line and a solid line in formulas (Ia) and (Ib).
- Is a single bond has a (meth) acryloyl group at one end and a butyl group at another end, and the content of the repeating unit represented by the formula (Ia) is a repeating unit constituting the main chain skeleton. It is 35 mol%, the content of (meth) acryloyl groups is 80 mol% at the end, and the content of butyl groups is 20 mol% at the end.
- Photocurable resin A-2 To 10 parts by mass of isophorone diisocyanate, 5.19 parts by mass of 4-HBA and 0.67 parts by mass of butanol were added and reacted at 70 ° C. for 3 hours to obtain an adduct having an NCO group at one end. 6.59 parts by mass of isophorone diisocyanate was mixed with 100 parts by mass of hydroxyl-terminated hydrogenated polybutadiene and reacted at 70 ° C. for 5 hours under a nitrogen atmosphere to obtain a urethane polymer having hydroxyl groups at both ends. When the NCO remaining amount becomes 0.1% or less, 10.45 parts by mass of the adduct body is added thereto, and these are reacted at 70 ° C. for 5 hours. The residual isocyanate is 0.1% or less. At that time, the reaction was terminated to obtain a photocurable resin A-2.
- the photocurable resin A-2 has a repeating unit represented by the above formula (Ia) and the formula (Ib) in the main chain skeleton, and is a double line consisting of a broken line and a solid line in the formula (Ia) and the formula (Ib).
- Is a single bond has a (meth) acryloyl group at one end and a butyl group at another end, and the content of the repeating unit represented by the formula (Ia) is a repeating unit constituting the main chain skeleton. It is 35 mol%, the content of (meth) acryloyl groups is 80 mol% at the end, and the content of butyl groups is 20 mol% at the end.
- Photocurable resin A-3 12.9 parts by mass of isophorone diisocyanate was mixed with 100 parts by mass of hydroxyl-terminated hydrogenated polybutadiene and reacted at 70 ° C. for 5 hours in a nitrogen atmosphere to obtain a urethane prepolymer having isocyanate groups at both ends.
- NCO remaining amount 0.99%
- 3.08 parts by mass of 4-HBA and 0.8 parts by mass of 2-ethylhexanol manufactured by Tokyo Chemical Industry Co., Ltd., boiling point 187 ° C.
- the reaction was terminated at 70 ° C. for 5 hours, and when the residual isocyanate was 0.1% or less, the reaction was terminated to obtain a photocurable resin A-3.
- the main chain skeleton has a repeating unit represented by the above formula (Ia) and the formula (Ib), and in the formula (Ia) and the formula (Ib), a double line consisting of a broken line and a solid line
- the line is a single bond, has a (meth) acryloyl group at one end and a 2-ethylhexyl group at another end, and the content of the repeating unit represented by the formula (Ia) constitutes the main chain skeleton It is 35 mol% of the repeating units, the content of (meth) acryloyl group is 80 mol% at the end, and the content of 2-ethylhexyl group is 20 mol% at the end.
- Photocurable resin A-4 To 10 parts by mass of isophorone diisocyanate, 3.24 parts by mass of 4-HBA and 3.56 parts by mass of decanol (KH neochem, boiling point 211 ° C., the same applies hereinafter) are added and reacted at 70 ° C. for 3 hours to have an NCO group at one end. An adduct body was obtained. 6.59 parts by mass of isophorone diisocyanate was mixed with 100 parts by mass of hydroxyl-terminated hydrogenated polybutadiene and reacted at 70 ° C. for 5 hours under a nitrogen atmosphere to obtain a urethane polymer having hydroxyl groups at both ends.
- the photocurable resin A-4 has a repeating unit whose main chain skeleton is represented by the above formulas (Ia) and (Ib), and is a double line consisting of a broken line and a solid line in the formulas (Ia) and (Ib).
- Is a single bond has a (meth) acryloyl group at one end and a decyl group at another end, and the content of the repeating unit represented by the formula (Ia) is a repeating unit constituting the main chain skeleton.
- the content of the (meth) acryloyl group is 50 mol% at the end, and the content of the decyl group is 50 mol% at the end.
- the photocurable resin A-5 has a main chain skeleton having repeating units represented by the above formulas (Ia) and (Ib), and a double line consisting of a broken line and a solid line in the formulas (Ia) and (Ib).
- Is a single bond has a (meth) acryloyl group at one end and a decyl group at another end, and the content of the repeating unit represented by the formula (Ia) is a repeating unit constituting the main chain skeleton.
- the content of the (meth) acryloyl group is 50 mol% at the end, and the content of the decyl group is 50 mol% at the end.
- Photocurable resin A-6 6.7 parts by mass of hexamethylene diisocyanate (50M-HDI, manufactured by Asahi Kasei Chemicals) is mixed with 100 parts by mass of hydroxyl-terminated hydrogenated polybutadiene, and reacted at 70 ° C. for 5 hours in a nitrogen atmosphere, so that isocyanate is present at both ends. A urethane prepolymer having a group was obtained. When the NCO remaining amount reached 0.72%, 1.06 parts by mass of 2-hydroxyethyl acrylate (manufactured by Osaka Organic Chemical Co., Ltd., the same applies below) and 1.45 parts by mass of decanol were added, and 70 ° C. The reaction was terminated when the residual isocyanate was 0.1% or less to obtain a photocurable resin A-6.
- 50M-HDI hexamethylene diisocyanate
- the photocurable resin A-6 has a main chain skeleton having repeating units represented by the above formulas (Ia) and (Ib), and a double line consisting of a broken line and a solid line in the formulas (Ia) and (Ib).
- Is a single bond has a (meth) acryloyl group at one end and a decyl group at another end, and the content of the repeating unit represented by the formula (Ia) is a repeating unit constituting the main chain skeleton.
- the content of the (meth) acryloyl group is 50 mol% at the end, and the content of the decyl group is 50 mol% at the end.
- the main chain skeleton has repeating units represented by the above formulas (Ia) and (Ib), and a double line consisting of a broken line and a solid line in the formulas (Ia) and (Ib).
- Is a single bond has a (meth) acryloyl group at one end and a butyl group at another end, and the content of the repeating unit represented by the formula (Ia) is a repeating unit constituting the main chain skeleton. It is 35 mol%, the content of (meth) acryloyl groups is 80 mol% at the end, and the content of butyl groups is 20 mol% at the end.
- the photocurable resin B-1 has a repeating unit represented by the above formula (IIa) and formula (IIb) in the main chain skeleton, and is a double line consisting of a broken line and a solid line in the formulas (IIa) and (IIb).
- Is a single bond has a (meth) acryloyl group at one end and a butyl group at another end, and the content of the repeating unit represented by the formula (IIa) is a repeating unit constituting the main chain skeleton. 15 mol%, the content of (meth) acryloyl groups is 80 mol% at the end, and the content of butyl groups is 20 mol% at the end.
- Photocurable resin A-8 Hydroxyl-terminated hydrogenated polybutadiene 1 (a linear polymer having a main chain skeleton having repeating units represented by the above formulas (Ia) and (Ib), and a broken line and a solid line in the formulas (Ia) and (Ib)) Is a single bond, the content of the repeating unit represented by the formula (Ia) is 35 mol% of the repeating unit constituting the main chain skeleton, and has hydroxyl groups at both ends.
- HLBH-P2000 (manufactured by Clay Valley Co., Ltd., the same shall apply hereinafter) 12.9 parts by mass of isophorone diisocyanate (manufactured by Evonik, the same shall apply hereinafter) is mixed with 100 parts by mass and reacted at 70 ° C. for 5 hours under a nitrogen atmosphere. A urethane prepolymer having an isocyanate group at the terminal was obtained.
- the main chain skeleton has repeating units represented by the above formulas (Ia) and (Ib), and a double line consisting of a broken line and a solid line in the formulas (Ia) and (Ib).
- Is a single bond has a (meth) acryloyl group at one end and a butoxyethyl group at another end, and the content of the repeating unit represented by the formula (Ia) constitutes the main chain skeleton
- the content of the (meth) acryloyl group is 80 mol% at the end and the content of butoxyethyl group is 20 mol% at the end.
- the main chain skeleton has repeating units represented by the above formulas (Ia) and (Ib), and in the formulas (Ia) and (Ib), a double line consisting of a broken line and a solid line Is a single bond, has a (meth) acryloyl group at one end and a 2-butoxyethyl group at another end, and the content of the repeating unit represented by the formula (Ia) constitutes the main chain skeleton It is 35 mol% of the repeating unit, the content of (meth) acryloyl group is 80 mol% at the end, and the content of 2-butoxyethyl group is 20 mol% at the end.
- Photocurable resin A-10 12.9 parts by mass of isophorone diisocyanate was mixed with 100 parts by mass of hydroxyl-terminated hydrogenated polybutadiene and reacted at 70 ° C. for 5 hours in a nitrogen atmosphere to obtain a urethane prepolymer having isocyanate groups at both ends.
- NCO remaining amount becomes 0.99%
- 3.08 parts by mass of 4-HBA and diethylene glycol monoethyl ether (Seafosol (registered trademark) DG, manufactured by Nippon Shokubai Co., Ltd., boiling point 202 ° C.) are added to the urethane prepolymer.
- 72 parts by mass was added and reacted at 70 ° C. for 5 hours.
- the residual isocyanate was 0.1% or less, the reaction was terminated to obtain a photocurable resin A-10.
- the main chain skeleton has repeating units represented by the above formulas (Ia) and (Ib), and in the formulas (Ia) and (Ib), a double line consisting of a broken line and a solid line is used.
- the line is a single bond, has a (meth) acryloyl group at one end and a 2- (2-ethoxyethoxy) ethyl group at another end, and the content of the repeating unit represented by the formula (Ia) is 35 mol% of the repeating unit constituting the main chain skeleton, the content of (meth) acryloyl group is 80 mol% of the terminal, and the content of 2- (2-ethoxyethoxy) ethyl group is 20 mol of the terminal %.
- the photocurable resin A-11 has a main chain skeleton having repeating units represented by the above formulas (Ia) and (Ib), and a double line consisting of a broken line and a solid line in the formulas (Ia) and (Ib).
- Is a single bond has a (meth) acryloyl group at one end and a 1-butoxy-2-propyl group at another end, and the content of the repeating unit represented by the formula (Ia) is the main chain skeleton
- the content of the (meth) acryloyl group is 50 mol% at the terminal, and the content of 1-butoxy-2-propyl group is 50 mol% at the terminal.
- Comparative photo-curing resin E-2 19.2 parts by mass of isophorone diisocyanate was mixed with 100 parts by mass of hydroxyl-terminated hydrogenated polybutadiene and reacted at 70 ° C. for 5 hours in a nitrogen atmosphere.
- the NCO remaining amount becomes 2.0%
- 3.35 parts by mass of 2-hydroxyethyl acrylate is added thereto, and when the NCO remaining amount becomes 1.0%
- isopropanol (Tokyo Chemical Industry, boiling point) (82.4 ° C.) 1.76 parts by mass were added and reacted at 70 ° C. for 5 hours to obtain a comparative photocurable resin E-2.
- the content of the repeating unit represented by the formula (IIa) is 15 mol% or less of the repeating units constituting the main chain skeleton. It does not fall under the resin of the present invention.
- the content of the repeating unit represented by the formula (IIa) is 15 mol% or less of the repeating unit constituting the main chain skeleton, has an acryloyl group at both ends, Since it does not have a non-photoreactive group, the comparative photocurable resin E-3 does not fall under the resin of the present invention.
- Comparative photo-curing resin E-4 12.9 parts by mass of isophorone diisocyanate was mixed with 100 parts by mass of hydroxyl-terminated hydrogenated polybutadiene and reacted at 70 ° C. for 5 hours in a nitrogen atmosphere to obtain a urethane prepolymer having isocyanate groups at both ends.
- NCO remaining amount becomes 0.99%
- 4-hydroxybutyl acrylate 3.89 parts by mass is added and reacted, and when the NCO remaining amount becomes 0.1% or less, the reaction is performed.
- a comparative photocurable resin E-4 was obtained.
- the comparative photocurable resin E-4 does not fall under the resin of the present invention because it has an acryloyl group at both ends and no non-photoreactive group at the ends.
- a durability test was performed by placing the initial adhesive sample prepared as described above in a high temperature and high humidity environment of 65 ° C. and 95% RH for 100 hours to obtain an adhesive sample after the durability test.
- the initial adhesive strength was measured by fixing one glass substrate of the initial adhesive sample obtained as described above and performing a tensile test on the other glass substrate at a tensile test speed of 5 mm / min. The maximum value when the glass substrates were peeled off was defined as the adhesive strength.
- the adhesive strength was measured in the same manner as described above to obtain the adhesive strength after 65 ° C. and 95%.
- the weather resistance was evaluated by the yellow index (YI).
- YI yellow index
- JIS K7350-2 an initial adhesion sample obtained as described above was subjected to a xenon weather meter under conditions of a wavelength of 300 to 400 nm, an irradiance of 180 W / m 2 , a black panel temperature of 83 ° C., and a humidity of 50% RH.
- a weather resistance test was performed in which light was irradiated for 100 hours.
- Monofunctional (meth) acrylate 1 dicyclopentenyl acrylate
- Monofunctional (meth) acrylate 2 isobornyl acrylate
- Monofunctional (meth) acrylate 3 isodecyl acrylate
- Comparative photo-curable resins E-1 to E-4 Comparative photo-curable resins produced as described above
- Photopolymerization initiator 1 Irgacure 184 (manufactured by BASF) Plasticizer 1: Polyethylene glycol di-2-ethylhexaate. Liquid at room temperature (trade name TegMeR 804, manufactured by Hallstar) Plasticizer 2: Polyethylene wax. It is liquid at room temperature. Versaflow EV (Shamrock Technologies, Inc.)
- Comparative Examples 1 to 3 had low adhesion strength retention and poor adhesion.
- the increase in YI could not be suppressed after the durability test, and the weather resistance was poor.
- Comparative Examples 3 and 4 which did not contain a predetermined photocurable resin and instead contained a photocurable resin having no non-photoreactive group had low adhesive strength retention and poor adhesion.
- the composition of the present invention has a high adhesive strength retention and excellent adhesiveness. Further, the composition of the present invention was able to suppress the increase in YI after the durability test, and was excellent in weather resistance.
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Abstract
Description
例えば、特許文献1には、ポリオール(a1)とポリイソシアネート(a2)との反応物であるイソシアネート基含有化合物[a]中のイソシアネート基が、水酸基含有(メタ)アクリレート(a3)の水酸基及び、飽和アルコール(a4)の水酸基と、それぞれウレタン結合を形成してなるポリイソシアネート系誘導体[A]、及びエチレン性不飽和単量体[B]を含有してなることを特徴とする活性エネルギー線硬化型粘着剤組成物が開示され、ポリオール(a1)として水添ポリブタジエンポリオール等が記載されている。
そこで、本発明は接着性に優れる光硬化性樹脂を提供することを目的とする。
また、本発明は、混合物、および、光硬化性樹脂組成物を提供することも目的とする。
本発明は上記知見等に基づくものであり、具体的には以下の構成により上記課題を解決するものである。
上記非光反応性基が、ヘテロ原子を有してもよい、飽和炭化水素基及び芳香族炭化水素基からなる群から選ばれる少なくとも1種であり、
前記非光反応性基の端部に、ヒドロキシ基、アミノ基、-CH=NH、カルボキシ基又はメルカプト基は結合せず、
上記式(Ia)で表される繰り返し単位の含有量が、上記主鎖骨格を構成する繰り返し単位の15モル%を超える量であり、
上記(メタ)アクリロイル基の含有量が、上記末端の5モル%以上であり、
上記非光反応性基の含有量が、上記末端の5モル%以上である、光硬化性樹脂。
式(Ia)又は式(Ib)中、破線と実線との二重線は単結合または二重結合を表す。
2. 上記非光反応性基が、エーテル結合を有してもよい、飽和炭化水素基である、上記1に記載の光硬化性樹脂。
3. 上記非光反応性基が、単官能アルコール、
1つのヒドロキシ基を有し、且つ、ヘテロ原子を有する、飽和炭化水素化合物、及び、
1つのヒドロキシ基を有し、且つ、ヘテロ原子を有してもよい、芳香族炭化水素化合物からなる群から選ばれる少なくとも1種のヒドロキシ化合物によって形成され、
上記ヒドロキシ化合物の沸点が、100℃以上である、上記1又は2に記載の光硬化性樹脂(ただし、上記飽和炭化水素化合物又は上記芳香族炭化水素化合物の端部において、上記ヘテロ原子は、ヒドロキシ基、アミノ基、-CH=NH、カルボキシ基又はメルカプト基を形成しない。)。
4. 上記式(Ia)で表される繰り返し単位の含有量が、上記主鎖骨格を構成する繰り返し単位の35モル%以下である、上記1~3のいずれかに記載の光硬化性樹脂。
5. 上記1~4のいずれかに記載の光硬化性樹脂と、
主鎖骨格が下記式(IIa)及び式(IIb)で表される繰り返し単位を有し、末端に(メタ)アクリロイル基及び非光反応性基を有し、
上記非光反応性基が、ヘテロ原子を有してもよい、飽和炭化水素基及び芳香族炭化水素基からなる群から選ばれる少なくとも1種であり、
前記非光反応性基の端部に、ヒドロキシ基、アミノ基、-CH=NH、カルボキシ基又はメルカプト基は結合せず、
上記式(IIa)で表される繰り返し単位の含有量が、上記主鎖骨格を構成する繰り返し単位の15モル%以下であり、
上記(メタ)アクリロイル基の含有量が、上記末端の5モル%以上であり、
上記非光反応性基の含有量が、上記末端の5モル%以上である光硬化性樹脂Bとを含有する、混合物。
式(IIa)又は式(IIb)中、破線と実線との二重線は単結合または二重結合を表す。
6. 上記1~4のいずれかに記載の光硬化性樹脂と、単官能(メタ)アクリレートと、光重合開始剤と、可塑剤とを含む、光硬化性樹脂組成物。
7. 更に、光硬化性樹脂Bを含み、
上記光硬化性樹脂Bが、主鎖骨格が下記式(IIa)及び式(IIb)で表される繰り返し単位を有し、末端に(メタ)アクリロイル基及び非光反応性基を有し、
上記非光反応性基が、ヘテロ原子を有してもよい、飽和炭化水素基及び芳香族炭化水素基からなる群から選ばれる少なくとも1種であり、
前記非光反応性基の端部に、ヒドロキシ基、アミノ基、-CH=NH、カルボキシ基又はメルカプト基は結合せず、
上記式(IIa)で表される繰り返し単位の含有量が、上記主鎖骨格を構成する繰り返し単位の15モル%以下であり、
上記(メタ)アクリロイル基の含有量が、上記末端の5モル%以上であり、
上記非光反応性基の含有量が、上記末端の5モル%以上である、上記6に記載の光硬化性樹脂組成物。
式(IIa)又は式(IIb)中、破線と実線との二重線は単結合または二重結合を表す。
また、本発明は、接着性に優れる、混合物および光硬化性樹脂組成物を提供することができる。
なお、本明細書において、(メタ)アクリレートはアクリレートまたはメタクリレートを表し、(メタ)アクリロイルはアクリロイルまたはメタクリロイルを表し、(メタ)アクリルはアクリルまたはメタクリルを表す。
また、本明細書において「~」を用いて表される数値範囲は、「~」の前後に記載される数値を下限値および上限値として含む範囲を意味する。
本明細書において、特に断りのない限り、各成分はその成分に該当する物質をそれぞれ単独でまたは2種以上を組み合わせて使用することができる。成分が2種以上の物質を含む場合、成分の含有量は、2種以上の物質の合計の含有量を意味する。
本発明の光硬化性樹脂(本発明の樹脂)は、
主鎖骨格が下記式(Ia)及び式(Ib)で表される繰り返し単位を有し、末端に(メタ)アクリロイル基及び非光反応性基を有し、
上記非光反応性基が、ヘテロ原子を有してもよい、飽和炭化水素基及び芳香族炭化水素基からなる群から選ばれる少なくとも1種であり、
前記非光反応性基の端部に、ヒドロキシ基、アミノ基、-CH=NH、カルボキシ基又はメルカプト基は結合せず、
上記式(Ia)で表される繰り返し単位の含有量が、上記主鎖骨格を構成する繰り返し単位の15モル%を超える量であり、
上記(メタ)アクリロイル基の含有量が、上記末端の5モル%以上であり、
上記非光反応性基の含有量が、上記末端の5モル%以上である、光硬化性樹脂である。
式(Ia)又は式(Ib)中、破線と実線との二重線は単結合または二重結合を表す。
本発明の樹脂は上記式(Ia)で表される繰り返し単位を多く含み、結晶性が高いため、例えば高温又は多湿などの外部の影響を受けにくいと考えられる。このため、上記式(Ia)で表される繰り返し単位の含有量が所定の範囲によって耐久試験後でも高い接着性を維持することができると推察される。
また、本発明の樹脂は、末端に非光反応性基を有し、上記末端では光反応しないことによって、硬化後に得られる硬化物に柔軟性を付与することができると考えられる。また、本発明の樹脂は、非光反応性基の端部に、ヒドロキシ基、アミノ基、-CH=NH、カルボキシ基又はメルカプト基を結合せず、上記端部では反応しないことによって、硬化後に得られる硬化物に柔軟性を付与することができると考えられる。このような柔軟性によって、本発明の樹脂は接着性に優れると推察する。
以下、本発明の樹脂について詳述する。
本発明において、上記主鎖骨格のミクロ構造は、主鎖骨格の原料ポリマー(例えば、末端に官能基を有する(水添)ポリブタジエン)のミクロ構造が反映される。
主鎖骨格の原料ポリマー(未水添)(例えば、末端に官能基を有するポリブタジエン)のミクロ構造は、赤外吸収スペクトル分析によって算出できる。具体的には、ミクロ構造に由来するピーク位置(cis:740cm-1、vinyl:910cm-1、trans:967cm-1)の吸収強度比から、主鎖骨格のミクロ構造を算出できる。
主鎖骨格の原料ポリマー(水素添加物)(例えば、末端に官能基を有する水添ポリブタジエン)のミクロ構造は、水素添加の原料として使用されたポリマー(例えば、末端に官能基を有するポリブタジエン)のミクロ構造と同じとできる。
本発明の樹脂は末端に(メタ)アクリロイル基及び非光反応性基を有し、
上記非光反応性基が、ヘテロ原子を有してもよい、飽和炭化水素基及び芳香族炭化水素基からなる群から選ばれる少なくとも1種である。
ただし、上記非光反応性基の端部に、ヒドロキシ基、アミノ基、-CH=NH、カルボキシ基又はメルカプト基は結合しない。
本発明において、非光反応性基は、光で反応しない基を意味する。
また、本発明において、光反応性基は、光で反応する基を意味する。光反応性基としては、(メタ)アクリロイル基、(メタ)アクリロイルオキシ基、ビニル基のようなエチレン性不飽和結合を有する基が挙げられる。
なお、本発明において、上記末端は上記主鎖骨格又は本発明の樹脂の末端を意味する。また、上記末端には、上記式(Ib)におけるエチル基又はビニル基は含まれない。
本発明の樹脂は末端を複数有することができる。本発明の樹脂は末端を2つ有することが好ましい態様の1つとして挙げられる。
1つの末端に(メタ)アクリロイル基又は非光反応性基を有することが好ましい態様の1つとして挙げられる。
本発明において、非光反応性基の端部は、本発明の樹脂の末端と同義である。
有機基は特に制限されない。有機基としては、例えば、ウレタン結合、エステル結合、炭化水素基が挙げられる。有機基は、ウレタン結合及びエステル結合からなる群から選ばれる少なくとも1種に結合する炭化水素基を有することが好ましい態様の1つとして挙げられる。
本発明の樹脂は(メタ)アクリロイル基を有することによって光硬化性(光反応性)を有する。
本発明において、(メタ)アクリロイル基は(メタ)アクリロイルオキシ基を含む。
本発明において、非光反応性基は、ヘテロ原子を有してもよい、飽和炭化水素基(直鎖状、分岐状又は環状を含む。)及び芳香族炭化水素基からなる群から選ばれる少なくとも1種である。
ただし、非光反応性基の端部に、ヒドロキシ基、アミノ基、-CH=NH、カルボキシ基又はメルカプト基は結合しない。
非光反応性基の全体に、ヒドロキシ基、アミノ基、-CH=NH、カルボキシ基又はメルカプト基が結合しないとできる。
非光反応性基は、ヘテロ原子を有さない、飽和炭化水素基及び芳香族炭化水素基からなる群から選ばれる少なくとも1種であってもよい。この場合、上記非光反応性基は、無置換の、飽和炭化水素基及び芳香族炭化水素基からなる群から選ばれる少なくとも1種となる。
非光反応性基が、ヘテロ原子を有する、飽和炭化水素基及び芳香族炭化水素基からなる群から選ばれる少なくとも1種である場合、硬化後に得られる硬化物に更に柔軟性を付与することができる。
非光反応性基が、ヘテロ原子を有する飽和炭化水素基を有し、上記飽和炭化水素基が有する任意の炭素原子(ただし、飽和炭化水素基の末端の炭素原子を除く。)を上記ヘテロ原子に置換した場合、上記非光反応性基において、上記ヘテロ原子よりも樹脂の末端側の端部(本発明の樹脂における、非光反応性基側の、末端)は、無置換の、アルキル基(直鎖状、分岐状、環状、又は、これらの組合せ)であることが好ましい。
上記ヘテロ原子は、上記飽和炭化水素基又は上記芳香族炭化水素基において、例えば、エーテル結合、第3級アミン結合(1個の窒素原子に3個の炭素原子が結合する)、チオエーテル結合、カルボニル結合、エステル結合、ウレタン結合を形成することができる。
非光反応性基がヘテロ原子を有する場合、上記非光反応性基は、柔軟性が向上し接着性により優れ、耐候性に優れるという観点から、エーテル結合、第3級アミン結合、チオエーテル結合、カルボニル結合、エステル結合及びウレタン結合からなる群から選ばれる少なくとも1種を有してもよい飽和炭化水素基が好ましく、エーテル結合を有してもよい飽和炭化水素基がより好ましい。
飽和炭化水素基としては、例えば、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基が挙げられる。上記飽和炭化水素基は直鎖状、分岐状又は環状の何れであってもよい。上記の飽和炭化水素基において任意の炭素原子がヘテロ原子に置換されてもよい。
分岐状の飽和炭化水素基としては、例えば、エチルヘキシル基、イソステアリル基が挙げられる。上記の分岐状の飽和炭化水素基において任意の炭素原子がヘテロ原子に置換されてもよい。
ヘテロ原子を有する飽和炭化水素基としては、例えば、ブトキシエチル基、ブトキシプロピル基のような、アルコキシアルキル基;エトキシエトキシエチル基のような、末端がアルキル基で封鎖された、ポリオキシアルキレン基が挙げられる。
ヘテロ原子を有する、飽和炭化水素基及び芳香族炭化水素基の組合せとしては、例えば、メトキシフェニル基のようなアルコキシフェニル基;2-フェノキシエチル基のような、芳香族炭化水素基で封鎖されたオキシアルキレン基;2-(2-フェノキシエトキシ)エチル基のような、芳香族炭化水素基で封鎖されたポリオキシアルキレン基が挙げられる。
非光反応性基が炭素数4以上の飽和炭化水素によって構成される場合、柔軟性が向上し、接着性により優れると考えられる。
1つのヒドロキシ基を有し、且つ、ヘテロ原子(上記1つのヒドロキシ基を構成する酸素原子以外。以下同様)を有する、飽和炭化水素化合物、及び、
1つのヒドロキシ基を有し、且つ、ヘテロ原子(上記1つのヒドロキシ基を構成する酸素原子以外。以下同様)を有してもよい、芳香族炭化水素化合物からなる群から選ばれる少なくとも1種のヒドロキシ化合物によって形成することができる。
ただし、上記飽和炭化水素化合物又は上記芳香族炭化水素化合物の端部(上記端部は、上記単官能アルコール、上記飽和炭化水素化合物又は上記芳香族炭化水素化合物における、1つのヒドロキシ基とは、別の端部である。)において、上記ヘテロ原子は、ヒドロキシ基、アミノ基、-CH=NH、カルボキシ基又はメルカプト基を形成しない。
また、上記単官能アルコール、上記飽和炭化水素化合物又は上記芳香族炭化水素化合物が有する1つのヒドロキシ基は、上記主鎖骨格と非光反応性基とを結合させるために消費されるので、上記1つのヒドロキシ基に由来するヒドロキシ基を、本発明の樹脂は有さない。また、上記1つのヒドロキシ基に由来するヒドロキシ基は、非光反応性基の端部に結合するヒドロキシ基とはならない。
上記ヒドロキシ化合物の沸点は、100℃以上であることが好ましく、100~350℃がより好ましく、100~250℃が更に好ましい。
非光反応性基が沸点100℃以上の単官能アルコールによって形成される場合、本発明の樹脂を製造する際、単官能アルコールが揮発しにくく、単官能アルコールがイソシアネート基と十分反応でき、残存イソシアネートを少なくすることができるため、変色しにくく、耐候性に優れると考えられる。
上記単官能アルコールの沸点は、100~350℃が好ましく、100~250℃がより好ましい。
沸点100℃以上の単官能アルコールとしては、例えば、ブタノール、ペンタノール、ヘキサノール、ヘプタノール、オクタノール、エチルヘキサノール、デカノールが挙げられる。
沸点が100℃以上であり、1つのヒドロキシ基を有し、且つ、ヘテロ原子を有する、飽和炭化水素化合物としては、例えば、エチレングリコールモノブチルエーテル、ブトキシプロパノールのような、アルコキレングリコールモノアルキルエーテル;ジエチレングリコールモノエチルエーテルのような、ポリアルキレングリコールモノアルキルエーテルが挙げられる。
なお、本発明において、上記末端は、本発明の樹脂1分子が有する末端の全量、又は、本発明の樹脂全体における末端の全量を意味する(以下同様)。
(メタ)アクリロイル基の含有量は、接着性により優れ、耐候性に優れるという観点から、末端の10~95モル%が好ましく、40~90モル%がより好ましい。
本発明において、主鎖骨格の末端(又は本発明の樹脂の末端)に対する上記(メタ)アクリロイル基の含有量は、主鎖骨格の末端に対する(メタ)アクリロイル基を導入するために使用された化合物のモル比、又は、(メタ)アクリロイル基を導入するために使用された化合物及び非光反応性基を導入するために使用された化合物の合計量に対する(メタ)アクリロイル基を導入するための化合物のモル比とできる。
非光反応性基の含有量は、接着性により優れ、耐候性に優れるという観点から、末端の5~90モル%が好ましく、10~60モル%がより好ましい。
本発明において、主鎖骨格の末端(又は本発明の樹脂の末端)に対する上記非光反応性基の含有量は、主鎖骨格の末端に対する非光反応性基を導入するために使用された化合物のモル比、又は、(メタ)アクリロイル基を導入するために使用された化合物及び非光反応性基を導入するために使用された化合物の合計量に対する非光反応性基を導入するために使用された化合物のモル比とできる。
式(1)において、R1はそれぞれ独立に主鎖骨格を表し、R2はそれぞれ独立に有機基を表し、R3は(メタ)アクリロイル基を有する有機基を表し、R4は非光反応性基を表し、mは1~9であり、nは1~9であり、kは0又は1~10である。
上記ウレタンプレポリマーに、例えば、ポリイソシアネートとヒドロキシ基及び(メタ)アクリレートを有する化合物とを反応させた化合物(反応の際のNCO/OH(モル比)は2/1が好ましい。)、並びに、ポリイソシアネートと上記ヒドロキシ化合物(例えば単官能アルコール)とを反応させた化合物(反応の際のNCO/OH(モル比)は2/1が好ましい。)を添加できる。
なお、本発明の樹脂は、(メタ)アクリロイル基又は非光反応性基の含有量が異なる樹脂を含んでもよい。
また、上記官能基末端ポリブタジエン又は官能基末端水添ポリブタジエンは、少なくとも2つの末端にそれぞれ官能基を有することが好ましい態様の1つとして挙げられる。上記官能基は同じ種類であってもよく、異なる種類であってもよい。
本発明の樹脂の製造方法において使用される、ヒドロキシ基及び(メタ)アクリロイル基を有する化合物としては、例えば、1つのヒドロキシ基と(メタ)アクリロイル基とを有する化合物が挙げられる。上記ヒドロキシ基及び(メタ)アクリロイル基は有機基に結合することができる。有機基は特に制限されない。上記化合物としては、例えば、ヒドロキシエチル(メタ)アクリレート、ヒドロキシブチル(メタ)アクリレートのような、ヒドロキシアルキル(メタ)アクリレートが挙げられる。
本発明の混合物は、
本発明の光硬化性樹脂と、
主鎖骨格が下記式(IIa)及び式(IIb)で表される繰り返し単位を有し、末端に(メタ)アクリロイル基及び非光反応性基を有し、
上記非光反応性基が、ヘテロ原子を有してもよい、飽和炭化水素基及び芳香族炭化水素基からなる群から選ばれる少なくとも1種であり、
上記非光反応性基の端部に、ヒドロキシ基、アミノ基、-CH=NH、カルボキシ基又はメルカプト基は結合せず、
上記式(IIa)で表される繰り返し単位の含有量が、上記主鎖骨格を構成する繰り返し単位の15モル%以下であり、
上記(メタ)アクリロイル基の含有量が、上記末端の5モル%以上であり、
上記非光反応性基の含有量が、上記末端の5モル%以上である光硬化性樹脂Bとを含有する、混合物である。
式(IIa)又は式(IIb)中、破線と実線との二重線は単結合または二重結合を表す。
本発明の混合物に含有される光硬化性樹脂は本発明の光硬化性樹脂であれば特に制限されない。
なお、本明細書において、本発明の光硬化性樹脂を光硬化性樹脂Aとも称する。
本発明の混合物に含有される光硬化性樹脂Bは、式(IIa)で表される繰り返し単位の含有量が主鎖骨格を構成する繰り返し単位の15モル%以下であること以外、光硬化性樹脂Aと同様することができる。なお、式(IIa)の構造は上記式(Ia)と同じであり、式(IIb)の構造は上記式(Ib)と同じである。
式(IIb)で表される繰り返し単位の含有量は、接着性により優れ、耐候性に優れるという観点から、主鎖骨格を構成する繰り返し単位の85モル%以上が好ましく、85~99モル%がより好ましい。
本発明の光硬化性樹脂組成物(本発明の組成物)は、本発明の光硬化性樹脂と、単官能(メタ)アクリレートと、光重合開始剤と、可塑剤とを含む、光硬化性樹脂組成物である。
本発明の組成物に含有される光硬化性樹脂は本発明の光硬化性樹脂(光硬化性樹脂A)であれば特に制限されない。
本発明の組成物に含有される単官能(メタ)アクリレートは、(メタ)アクリロイルオキシ基を1個有する化合物であれば特に制限されない。(メタ)アクリロイルオキシ基は有機基に結合することができる。有機基は特に制限されない。
上記光重合開始剤としては、例えば、アルキルフェノン系化合物、ベンゾインエーテル系化合物、ベンゾフェノン系化合物のようなカルボニル化合物、硫黄化合物、アゾ化合物、パーオキサイド化合物、ホスフィンオキサイド系化合物等が挙げられる。
より具体的には、例えば、アセトフェノン、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、アセトイン、ブチロイン、トルオイン、ベンジル、ベンゾフェノン、p-メトキシベンゾフェノン、ジエトキシアセトフェノン、α,α-ジメトキシ-α-フェニルアセトフェノン、メチルフェニルグリオキシレート、エチルフェニルグリオキシレート、4,4′-ビス(ジメチルアミノベンゾフェノン)、2-ヒドロキシ-2-メチル-1-フェニルプロパン-1-オン、1-ヒドロキシシクロヘキシルフェニルケトンなどのカルボニル化合物;テトラメチルチウラムモノスルフィド、テトラメチルチウラムジスルフィドなどの硫黄化合物;アゾビスイソブチロニトリル、アゾビス-2,4-ジメチルバレロなどのアゾ化合物;ベンゾイルパーオキサイド、ジターシャリーブチルパーオキサイドなどのパーオキサイド化合物:等が挙げられ、これらを1種単独で用いてもよく、2種以上を併用してもよい。
1-ヒドロキシシクロヘキシルフェニルケトンの市販品としては、例えば、イルガキュア184(チバスペシャリティケミカルズ社製)が挙げられる。
本発明の組成物に含有される可塑剤は特に制限されない。例えば、室温で液状であるものが好ましい態様の1つとして挙げられる。
具体的な化合物として例えば、ポリエチレングリコール ジ2-エチルヘキサエートのようなポリオキシアルキレンポリオールのエステル;ポリエチレンワックスのようなポリオレフィンが挙げられる。
可塑剤の含有量は、上記光硬化性樹脂A等100質量部に対して、5~100質量部が好ましく、10~30質量部がより好ましい。
本発明の組成物は更に、光硬化性樹脂Bを含むことができる。
本発明の組成物が更に含むことができる光硬化性樹脂Bは、本発明の混合物に含有される光硬化性樹脂Bと同様である。
本発明の組成物は、本発明の目的を損なわない範囲で添加剤を更に含有することができる。添加剤としては、例えば、光硬化性樹脂A及びB以外のポリマー、充填剤、老化防止剤、酸化防止剤、帯電防止剤、難燃剤、接着性付与剤、レベリング剤、分散剤、消泡剤、艶消し剤、光安定剤(例えば、ヒンダードアミン系化合物等)、染料、顔料等が挙げられる。
本発明の組成物はその製造方法について特に限定されない。例えば、上記の各必須成分と任意成分とを、減圧下で混合ミキサー等のかくはん機を用いて混合する方法等によって本発明の組成物を製造することができる。
本発明の組成物に光を照射する際、光の波長は200~400nmとすることができる。また光量は100~300mW/cm2、積算光量は1000~3000mJ/cm2とすることができる。
光を照射するために使用する装置は特に制限されない。
本発明の組成物を硬化させる際の温度条件は特に制限されない。例えば、0~150℃とすることができる。
本発明の組成物を適用することができる基材(被着体)は特に制限されない。例えば、ガラス、プラスチック、ゴム、金属が挙げられる。
本発明の組成物を具体的には例えば光学用透明樹脂(OCR:Optical Clear Resin)とすることができる。OCRは例えば、タッチパネルのカバーガラス、透明導電部材、液晶モジュールなどを貼り合せることができる。
<本発明の樹脂の製造>
(光硬化性樹脂A-1)
水酸基末端水添ポリブタジエン1(主鎖骨格が上記式(Ia)及び式(Ib)で表される繰り返し単位を有する直鎖状のポリマーであり、式(Ia)及び式(Ib)において破線と実線との二重線は単結合であり、式(Ia)で表される繰り返し単位の含有量が主鎖骨格を構成する繰り返し単位の35モル%であり、両末端にヒドロキシ基を有する。商品名HLBH-P2000、クレイバレー社製。以下同様)100質量部に対し、イソホロンジイソシアネート(Evonik社製。以下同様)12.9質量部を混合し、窒素雰囲気下70℃で5時間反応させて、両末端にイソシアネート基を有するウレタンプレポリマーを得た。NCO残量が0.99%となった時点で、上記ウレタンプレポリマーに4-ヒドロキシブチルアクリレート(4-HBA。大阪有機化学社製。以下同様)3.08質量部及びブタノール(東京化成工業社製、沸点117℃)0.39質量部を添加し、70℃の条件下で5時間反応させ、残存イソシアネートが0.1%以下となった時点で反応を終了し、光硬化性樹脂A-1を得た。
イソホロンジイソシアネート10質量部に対し、4-HBA5.19質量部及びブタノール0.67質量部を添加し70℃3時間反応させ、片末端にNCO基を有するアダクト体を得た。
水酸基末端水添ポリブタジエン1:100質量部に対しイソホロンジイソシアネート6.59質量部を混合し、窒素雰囲気下70℃で5時間反応させて、両末端に水酸基を有するウレタンポリマーを得た。NCO残量が0.1%以下となった時点で、ここに上記アダクト体10.45質量部を添加し、これらを70℃の条件下で5時間反応させ、残存イソシアネートが0.1%以下となった時点で反応を終了し、光硬化性樹脂A-2を得た。
水酸基末端水添ポリブタジエン1:100質量部に対しイソホロンジイソシアネート12.9質量部を混合し、窒素雰囲気下70℃で5時間反応させて、両末端にイソシアネート基を有するウレタンプレポリマーを得た。NCO残量が0.99%となった時点で、上記ウレタンプレポリマーに4-HBA3.08質量部及び2-エチルヘキサノール(東京化成工業社製、沸点187℃)0.8質量部を添加し、70℃の条件下で5時間反応させ、残存イソシアネートが0.1%以下となった時点で反応を終了し、光硬化性樹脂A-3を得た。
イソホロンジイソシアネート10質量部に対し、4-HBA3.24質量部及びデカノール(KHネオケム、沸点211℃。以下同様)3.56質量部を添加し70℃3時間反応させ、片末端にNCO基を有するアダクト体を得た。
水酸基末端水添ポリブタジエン1:100質量部に対しイソホロンジイソシアネート6.59質量部を混合し、窒素雰囲気下70℃で5時間反応させて、両末端に水酸基を有するウレタンポリマーを得た。NCO残量が0.1%以下となった時点で、ここに上記アダクト体11.08質量部を添加し、これらを70℃で5時間反応させ、残存イソシアネートが0.1%以下となった時点で反応を終了し、光硬化性樹脂A-4を得た。
水酸基末端水添ポリブタジエン2(主鎖骨格が上記式(Ia)及び式(Ib)で表される繰り返し単位を有する直鎖状のポリマーであり、式(Ia)及び式(Ib)において破線と実線との二重線は単結合であり、式(Ia)で表される繰り返し単位の含有量が主鎖骨格を構成する繰り返し単位の35モル%であり、両末端にヒドロキシ基を有する。商品名HLBH-P3000、クレイバレー社製)100質量部に対しイソホロンジイソシアネート8.8質量部を混合し、窒素雰囲気下70℃で5時間反応させて、両末端にイソシアネート基を有するウレタンプレポリマーを得た。NCO残量が0.71%となった時点で、上記ウレタンプレポリマーに4-HBA1.33質量部、デカノール1.33質量部を添加し、70℃で5時間反応させ、残存イソシアネートが0.1%以下となった時点で反応を終了し、光硬化性樹脂A-5を得た。
水酸基末端水添ポリブタジエン2:100質量部に対しヘキサメチレンジイソシアネート(50M-HDI、旭化成ケミカルズ社製)6.7質量部を混合し、窒素雰囲気下70℃で5時間反応させて、両末端にイソシアネート基を有するウレタンプレポリマーを得た。NCO残量が0.72%となった時点で、時点で、2-ヒドロキシエチルアクリレート(大阪有機化学社製。以下同様)1.06質量部及びデカノール1.45質量部を添加し、70℃で5時間反応させ、残存イソシアネートが0.1%以下となった時点で反応を終了し、光硬化性樹脂A-6を得た。
水酸基末端水添ポリブタジエン2:100質量部及び水酸基末端水添ポリブタジエン3(商品名GI-2000、日本曹達社製。上記式(IIa)及び式(IIb)で表される繰り返し単位を有し、式(IIa)及び式(IIb)において破線と実線との二重線は単結合であり、式(IIa)で表される繰り返し単位の含有量が主鎖骨格を構成する繰り返し単位の15モル%であり、両末端にヒドロキシ基を有する。以下同様)20質量部に対し、イソホロンジイソシアネート11.2質量部を配合し、窒素雰囲気下70℃で5時間反応させて、両末端にイソシアネート基を有するウレタンプレポリマーを得た。NCO残量が0.74%となった時点で、上記ウレタンプレポリマーに2-ヒドロキシエチルアクリレート2.15質量部及びブタノール0.53質量部を添加し、70℃で5時間反応させ、残存イソシアネートが0.1%以下となった時点で反応を終了し、光硬化性樹脂A-7と光硬化性樹脂B-1とを含有する混合物1を得た。
水酸基末端水添ポリブタジエン1(主鎖骨格が上記式(Ia)及び式(Ib)で表される繰り返し単位を有する直鎖状のポリマーであり、式(Ia)及び式(Ib)において破線と実線との二重線は単結合であり、式(Ia)で表される繰り返し単位の含有量が主鎖骨格を構成する繰り返し単位の35モル%であり、両末端にヒドロキシ基を有する。商品名HLBH-P2000、クレイバレー社製。以下同様)100質量部に対し、イソホロンジイソシアネート(Evonik社製。以下同様)12.9質量部を混合し、窒素雰囲気下70℃で5時間反応させて、両末端にイソシアネート基を有するウレタンプレポリマーを得た。NCO残量が0.99%となった時点で、上記ウレタンプレポリマーに4-ヒドロキシブチルアクリレート(4-HBA。大阪有機化学社製。以下同様)3.08質量部及びエチレングリコールモノブチルエーテル(東京化成株式会社製、沸点171℃。以下同様)0.63量部を添加し、70℃の条件下で5時間反応させ、残存イソシアネートが0.1%以下となった時点で反応を終了し、光硬化性樹脂A-8を得た。
イソホロンジイソシアネート10質量部に対し、4-HBA5.19質量部及びエチレングリコールモノブチルエーテル1.06量部を添加し70℃3時間反応させ、片末端にNCO基を有するアダクト体を得た。
水酸基末端水添ポリブタジエン1:100質量部に対しイソホロンジイソシアネート6.59質量部を混合し、窒素雰囲気下70℃で5時間反応させて、両末端に水酸基を有するウレタンポリマーを得た。NCO残量が0.1%以下となった時点で、ここに上記アダクト体10.72質量部を添加し、これらを70℃の条件下で5時間反応させ、残存イソシアネートが0.1%以下となった時点で反応を終了し、光硬化性樹脂A-9を得た。
水酸基末端水添ポリブタジエン1:100質量部に対しイソホロンジイソシアネート12.9質量部を混合し、窒素雰囲気下70℃で5時間反応させて、両末端にイソシアネート基を有するウレタンプレポリマーを得た。NCO残量が0.99%となった時点で、上記ウレタンプレポリマーに4-HBA3.08質量部及びジエチレングリコールモノエチルエーテル(シーホゾール(登録商標)DG、日本触媒社製、沸点202℃)0.72質量部を添加し、70℃の条件下で5時間反応させ、残存イソシアネートが0.1%以下となった時点で反応を終了し、光硬化性樹脂A-10を得た。
イソホロンジイソシアネート10質量部に対し、4-HBA3.24質量部及び1-ブトキシ-2-プロパノール(東京化成株式会社製、沸点170℃。以下同様)2.97質量部を添加し70℃3時間反応させ、片末端にNCO基を有するアダクト体を得た。
水酸基末端水添ポリブタジエン1:100質量部に対しイソホロンジイソシアネート6.59質量部を混合し、窒素雰囲気下70℃で5時間反応させて、両末端に水酸基を有するウレタンポリマーを得た。NCO残量が0.1%以下となった時点で、ここに上記アダクト体10.69質量部を添加し、これらを70℃で5時間反応させ、残存イソシアネートが0.1%以下となった時点で反応を終了し、光硬化性樹脂A-11を得た。
水酸基末端水添ポリブタジエン3:100質量部及び水酸基末端水添ポリブタジエン4(GI-1000、日本曹達社製。上記式(IIa)及び式(IIb)で表される繰り返し単位を有し、式(IIa)及び式(IIb)において破線と実線との二重線は単結合であり、式(IIa)で表される繰り返し単位の含有量が主鎖骨格を構成する繰り返し単位の15モル%であり、両末端にヒドロキシ基を有する。)70質量部に対しイソホロンジイソシアネート26.9質量部を混合し、窒素雰囲気下70℃で5時間反応させた。NCO残量が1.7%となった時点で、ここに4-ヒドロキシブチルアクリレート5.8質量部を添加し、NCO残量が0.8%となった時点でメタノール(東京化成工業、沸点64.7℃)1.29質量部を添加し、70℃で5時間反応させ、残存イソシアネートが0.3%となった時点で反応を終了し、比較光硬化性樹脂E-1を得た。
比較光硬化性樹脂E-1において、式(IIa)で表される繰り返し単位の含有量は主鎖骨格を構成する繰り返し単位の15モル%以下であるので、比較光硬化性樹脂E-1は本発明の樹脂に該当しない。
水酸基末端水添ポリブタジエン4:100質量部に対しイソホロンジイソシアネート19.2質量部を混合し、窒素雰囲気下70℃で5時間反応させた。NCO残量が2.0%となった時点で、ここに2-ヒドロキシエチルアクリレート3.35質量部を添加し、NCO残量が1.0%となった時点でイソプロパノール(東京化成工業、沸点82.4℃)1.76質量部を添加し、70℃で5時間反応させ、比較光硬化性樹脂E-2を得た。
比較光硬化性樹脂E-2において、式(IIa)で表される繰り返し単位の含有量は主鎖骨格を構成する繰り返し単位の15モル%以下であるので、比較光硬化性樹脂E-2は本発明の樹脂に該当しない。
水酸基末端水添ポリブタジエン3:100質量部及びイソホロンジイソシアネート11.7質量部を混合し、窒素雰囲気下70℃で5時間反応させた。NCO残量が0.91%となった時点で、ここに4-ヒドロキシブチルアクリレート5.8質量部を添加して反応させ、NCO残量が0.1%以下となった時点で反応を終了し、比較光硬化性樹脂E-3を得た。
比較光硬化性樹脂E-3において、式(IIa)で表される繰り返し単位の含有量は主鎖骨格を構成する繰り返し単位の15モル%以下であり、両末端にアクリロイル基を有し、末端に非光反応性基を有さないので、比較光硬化性樹脂E-3は本発明の樹脂に該当しない。
水酸基末端水添ポリブタジエン1:100質量部に対しイソホロンジイソシアネート12.9質量部を混合し、窒素雰囲気下70℃で5時間反応させて、両末端にイソシアネート基を有するウレタンプレポリマーを得た。NCO残量が0.99%となった時点で、ここに4-ヒドロキシブチルアクリレート:3.89質量部を添加して反応させ、NCO残量が0.1%以下となった時点で反応を終了し、比較光硬化性樹脂E-4を得た。
比較光硬化性樹脂E-4は、両末端にアクリロイル基を有し、末端に非光反応性基を有さないので、本発明の樹脂に該当しない。
下記第1表の各成分を同表に示す組成(質量部)で用いて、これらを撹拌機で混合し、組成物を製造した。
上記のとおり製造された各組成物を用いて以下の評価を行った。結果を第1表に示す。
(初期接着サンプル)
2枚のガラス基板(長さ25mm、幅25mm)を準備し、上記のとおり製造された各組成物を直径5mm、接着厚み0.3mmとなるように1枚のガラス基板に塗布し、上記ガラス基板と別のガラス基板とが十文字になるようにこれらを貼り合わせた後、以下の硬化条件で各組成物を硬化させ、初期接着サンプルを作製した。
光照射装置(GS UVSYSTEM TYPE S250―01、ジーエス・ユアサ ライティング社製)を用い、光源としてメタルハライドランプを使用し、波長250~380nmの紫外線を光量150mW/cmで積算光量2000mJ/cm2となるよう照射した。
上記のとおり作製した初期接着サンプルを65℃、95%RHの高温高湿環境下に100時間置く耐久性試験を行って、耐久性試験後接着サンプルを得た。
初期接着強度は、上記のとおり得られた初期接着サンプルの一方のガラス基板を固定して、他のガラス基板を引張り試験速度5mm/minにて引張り試験を行って測定された。ガラス基板同士が剥がれたときの最大値を接着強度とした。
耐久性試験後接着サンプルについても上記と同様にして接着強度を測定し、65℃95%後接着強度を得た。
接着強度保持率は下記式によって求められた。
接着強度保持率(%)=(65℃95%後接着強度/初期接着強度)×100
接着強度保持率が高いほど接着性に優れる。
耐候性はイエローインデックス(YI)で評価された。
(耐候性試験)
JIS K7350-2に準拠して、上記のとおり得られた初期接着サンプルに、キセノンウェザーメーターで、波長300~400nm、放射照度180W/m2、ブラックパネル温度83℃、湿度50%RHの条件で、100時間、光を照射する耐候性試験を行った。
JIS K7373:2006に準じて、上記サンプルについて、耐候性試験前後でYIを測定した。
耐候性試験前後でYIの上昇が小さいほど、耐候性に優れる。
・光硬化性樹脂A-1~6、8~10:上記のとおり製造された光硬化性樹脂
・混合物1:上記のとおり製造された混合物
・単官能(メタ)アクリレート2:イソボルニルアクリレート
・単官能(メタ)アクリレート3:イソデシルアクリレート
・可塑剤1:ポリエチレングリコール ジ2-エチルヘキサエート。室温で液状(商品名TegMeR 804、Hallstar社製)
・可塑剤2:ポリエチレンワックス。室温で液状である。Versaflow EV(Shamrock Technologies, Inc製)
所定の光硬化性樹脂を含有せず、代わりに非光反応性基を有さない光硬化性樹脂を含有する比較例3、4は、接着強度保持率が低く、接着性が悪かった。
また本発明の組成物は耐久性試験後においてYIの上昇を抑制することができ、耐候性に優れた。
Claims (7)
- 主鎖骨格が下記式(Ia)及び式(Ib)で表される繰り返し単位を有し、末端に(メタ)アクリロイル基及び非光反応性基を有し、
前記非光反応性基が、ヘテロ原子を有してもよい、飽和炭化水素基及び芳香族炭化水素基からなる群から選ばれる少なくとも1種であり、
前記非光反応性基の端部に、ヒドロキシ基、アミノ基、-CH=NH、カルボキシ基又はメルカプト基は結合せず、
前記式(Ia)で表される繰り返し単位の含有量が、前記主鎖骨格を構成する繰り返し単位の15モル%を超える量であり、
前記(メタ)アクリロイル基の含有量が、前記末端の5モル%以上であり、
前記非光反応性基の含有量が、前記末端の5モル%以上である、光硬化性樹脂。
式(Ia)又は式(Ib)中、破線と実線との二重線は単結合または二重結合を表す。 - 前記非光反応性基が、エーテル結合を有してもよい、飽和炭化水素基である、請求項1に記載の光硬化性樹脂。
- 前記非光反応性基が、単官能アルコール、
1つのヒドロキシ基を有し、且つ、ヘテロ原子を有する、飽和炭化水素化合物、及び、
1つのヒドロキシ基を有し、且つ、ヘテロ原子を有してもよい、芳香族炭化水素化合物からなる群から選ばれる少なくとも1種のヒドロキシ化合物によって形成され、
前記ヒドロキシ化合物の沸点が、100℃以上である、請求項1又は2に記載の光硬化性樹脂。(ただし、前記飽和炭化水素化合物又は前記芳香族炭化水素化合物の端部において、前記ヘテロ原子は、ヒドロキシ基、アミノ基、-CH=NH、カルボキシ基又はメルカプト基を形成しない。) - 前記式(Ia)で表される繰り返し単位の含有量が、前記主鎖骨格を構成する繰り返し単位の35モル%以下である、請求項1~3のいずれか1項に記載の光硬化性樹脂。
- 請求項1~4のいずれか1項に記載の光硬化性樹脂と、
主鎖骨格が下記式(IIa)及び式(IIb)で表される繰り返し単位を有し、末端に(メタ)アクリロイル基及び非光反応性基を有し、
前記非光反応性基が、ヘテロ原子を有してもよい、飽和炭化水素基及び芳香族炭化水素基からなる群から選ばれる少なくとも1種であり、
前記非光反応性基の端部に、ヒドロキシ基、アミノ基、-CH=NH、カルボキシ基又はメルカプト基は結合せず、
前記式(IIa)で表される繰り返し単位の含有量が、前記主鎖骨格を構成する繰り返し単位の15モル%以下であり、
前記(メタ)アクリロイル基の含有量が、前記末端の5モル%以上であり、
前記非光反応性基の含有量が、前記末端の5モル%以上である光硬化性樹脂Bとを含有する、混合物。
式(IIa)又は式(IIb)中、破線と実線との二重線は単結合または二重結合を表す。 - 請求項1~4のいずれか1項に記載の光硬化性樹脂と、単官能(メタ)アクリレートと、光重合開始剤と、可塑剤とを含む、光硬化性樹脂組成物。
- 更に、光硬化性樹脂Bを含み、
前記光硬化性樹脂Bが、主鎖骨格が下記式(IIa)及び式(IIb)で表される繰り返し単位を有し、末端に(メタ)アクリロイル基及び非光反応性基を有し、
前記非光反応性基が、ヘテロ原子を有してもよい、飽和炭化水素基及び芳香族炭化水素基からなる群から選ばれる少なくとも1種であり、
前記非光反応性基の端部に、ヒドロキシ基、アミノ基、-CH=NH、カルボキシ基又はメルカプト基は結合せず、
前記式(IIa)で表される繰り返し単位の含有量が、前記主鎖骨格を構成する繰り返し単位の15モル%以下であり、
前記(メタ)アクリロイル基の含有量が、前記末端の5モル%以上であり、
前記非光反応性基の含有量が、前記末端の5モル%以上である、請求項6に記載の光硬化性樹脂組成物。
式(IIa)又は式(IIb)中、破線と実線との二重線は単結合または二重結合を表す。
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JP2020152855A (ja) * | 2019-03-22 | 2020-09-24 | 横浜ゴム株式会社 | 熱硬化性樹脂組成物及び熱硬化性樹脂 |
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KR102187527B1 (ko) * | 2018-10-30 | 2020-12-07 | 주식회사 엘지화학 | 점착제 조성물 및 이의 경화물을 포함하는 점착제 |
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