WO2012081483A1 - 反応性可塑剤、およびこれを含む硬化性組成物 - Google Patents
反応性可塑剤、およびこれを含む硬化性組成物 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
- C09J171/02—Polyalkylene oxides
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- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/42—Introducing metal atoms or metal-containing groups
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- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
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- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
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- 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
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/22—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the initiator used in polymerisation
- C08G2650/24—Polymeric initiators
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Definitions
- the present invention relates to a reactive plasticizer containing a reactive silicon group. Furthermore, this invention relates to the curable composition which combined the organic polymer containing a reactive silicon group, and said reactive plasticizer.
- An organic polymer containing at least one reactive silicon group in the molecule is crosslinked at the room temperature by forming a siloxane bond accompanied by a hydrolysis reaction of the reactive silicon group due to moisture, etc. It is known to have the property that can be obtained.
- the main chain skeleton is a polyoxyalkylene polymer, a saturated hydrocarbon polymer, and a poly (meth) acrylate copolymer.
- Patent Document 1 and the like are already industrially produced and widely used in applications such as sealing materials, adhesives, coating materials, paints, and the like.
- the so-called reactive plasticizer having a reactive silicon group at the terminal or main chain of the high molecular weight plasticizer reacts with an organic polymer having a reactive silicon group, so that bleedout hardly occurs after curing.
- the introduction rate of the silicon group with respect to the terminal remains at most 80%, and the component to which the silicon group is not introduced remains, so that the effect of improving the bleed out is limited.
- the sealing material for construction needs to follow even if the wall material expands and contracts due to the influence of temperature or the like, it is desirable that it has a low modulus, a high elongation and a high resilience.
- a cured product of a curable composition containing an organic polymer having a reactive silicon group to exhibit physical properties of low modulus and high elongation.
- One method is to increase the amount of the plasticizer, but there is a problem that the restorability is lowered and the weather resistance of the cured product is lowered.
- the object of the present invention is to provide a curable composition that can be used mainly as a sealing material for buildings and has improved contamination to peripheral base materials such as stone and paint.
- Another object of the present invention is to provide a curable composition having a high resilience capable of following a joint having a large movement.
- the inventors of the present invention are organic polymers in which a reactive silicon group is introduced at one end, and in particular to peripheral substrates and paints by increasing the amount of silicon groups introduced. I found that I could solve the pollution problem. Furthermore, by using the organic polymer having the specific functional group, the inventors have found a feature that the restorability is improved and completed the present invention.
- the number average molecular weight is 800 to 15,000, and the general formula (1): —YR 1 —CH (CH 3 ) —CH 2 —Si (R 2 3-a ) X a (1)
- R 1 represents a divalent organic group having 1 to 20 carbon atoms containing at least one selected from the group consisting of hydrogen, carbon, and nitrogen as a constituent atom
- R 2 represents from 1 carbon atom.
- the main chain of the organic polymer (A) is linear, the organic polymer according to (I), (III).
- any of (I) to (VI), wherein the main chain of the organic polymer (A) is one or more of a polyoxyalkylene polymer, a polyacrylic polymer, and a hydrocarbon polymer The organic polymer according to (VIII).
- the organic polymer (A) is converted into a polyoxypropylene polymer obtained by reacting propylene oxide in the presence of a double metal cyanide complex catalyst using an initiator having only one hydroxyl group in one molecule.
- the organic polymer (A) is a combination of an initiator having two or more hydroxyl groups in one molecule and an initiator having only one hydroxyl group in one molecule, and propylene oxide is produced in the presence of a double metal cyanide complex catalyst.
- the organic polymer according to any one of (I) to (IX) which is obtained by introducing a reactive silicon group represented by the general formula (1) into a reacted polyoxypropylene polymer. Coalescence, (XI).
- the organic polymer (A) according to any one of (I) to (XI) and a number average molecular weight of 5,000 to 50,000 and an average of 1.2 reactive silicon groups in one molecule A curable composition comprising 5 to 5 organic polymers (B), (XIII).
- a water-based acrylic emulsion paint (trade name “please coat”, manufactured by SK Kaken Co., Ltd.) is applied to the surface of the sheet, and is further left for 7 days under conditions of 23 ° C. and 50% RH. After standing for 7 days, 67 black made by Shinto Porcelain Co., Ltd. is applied uniformly as a silica sand on the surface of the sheet. After 3 hours, measure the adhesion amount (mg / cm 2 ) per unit area when the silica sand is gently wiped with a brush. About.
- the main chain skeleton of the organic polymer (A) and organic polymer (B) having a reactive silicon group used in the present invention is not particularly limited, and those having various main chain skeletons can be used. It is preferable that the composition is composed of one or more selected from a hydrogen atom, a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom because the composition is excellent in curability and adhesiveness.
- polyoxyalkylene heavy polymers such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene-polyoxybutylene copolymer, etc.
- Saturated hydrocarbon polymers such as polyisobutylene, hydrogenated polyisoprene and hydrogenated polybutadiene, polyoxyalkylene polymers, and (meth) acrylic acid ester polymers have a relatively low glass transition temperature, and the resulting cured product Is more preferable because of its excellent cold resistance.
- the glass transition temperature of the organic polymer as component (A) and component (B) is not particularly limited, but is preferably 20 ° C. or lower, more preferably 0 ° C. or lower, and ⁇ 20 ° C. or lower. It is particularly preferred. If the glass transition temperature exceeds 20 ° C., the viscosity in winter or in a cold region may increase and workability may deteriorate, and the flexibility of the cured product may decrease and elongation may decrease.
- the glass transition temperature is a value obtained by DSC measurement.
- polyoxyalkylene polymers and (meth) acrylic acid ester polymers are particularly preferable because they have high moisture permeability and are excellent in deep-part curability when made into a one-component composition, and also in excellent adhesiveness.
- a polyoxyalkylene polymer is most preferred.
- polyoxypropylene polymers are particularly preferable.
- the reactive silicon group contained in the organic polymer (A) of the present invention has a hydroxy group or a hydrolyzable group bonded to a silicon atom, and forms a siloxane bond by a reaction accelerated by a silanol condensation catalyst. This is a group that can be crosslinked.
- the reactive silicon group the general formula (1): —YR 1 —CH (CH 3 ) —CH 2 —Si (R 2 3-a ) X a (1)
- R 1 represents a divalent organic group having 1 to 20 carbon atoms containing at least one selected from the group consisting of hydrogen, carbon, and nitrogen as a constituent atom
- R 2 represents from 1 carbon atom.
- R ′ is 1 to 20 carbon atoms.
- three R's may be the same or different, and X represents a hydroxyl group or a hydrolyzable group, and when two or more Xs are present, they are Y may be the same or different, Y is a heteroatom, selected from an oxygen atom or a nitrogen atom, and a is an integer of 1 to 3.
- an allyl group is introduced at the end of a polymer having a high molecular weight, and in the subsequent step, a silane such as methyldimethoxysilane or trimethoxysilane in the presence of a platinum catalyst. The compound is reacted. At this time, about 20% of the allyl group is internally isomerized and remains as a structure that does not react with the silane compound. It has been found that the molecular component that does not contain a silicon group remains as a reason why the prevention of contamination to the surroundings cannot be completely improved.
- the present invention improves the above problems by using a methallyl group that does not cause internal transition instead of an allyl group. Moreover, it discovered that the (A) component silylated using this methallyl group had the characteristics that it was highly recoverable compared with what was manufactured with the conventional manufacturing method silylated using an allyl group.
- a technique in which a methallyl group is introduced at both ends of a high molecular weight or at all ends of a branched main chain and a silicon group is introduced at almost all ends is known.
- a silicon group is introduced only at one end of an organic polymer having a linear main chain, and the performance as a reactive plasticizer is enhanced by increasing the introduction rate of the silicon group.
- the average number of silicon groups in this polymer is preferably less than 0.5 to 1.2 per molecule, more preferably 0.8 to 1.1, and 0.95 to 1.05. Most preferred.
- the reactive silicon group contained in the organic polymer (B) of the present invention has a hydroxy group or a hydrolyzable group bonded to a silicon atom, and forms a siloxane bond by a reaction accelerated by a silanol condensation catalyst. This is a group that can be crosslinked.
- the reactive silicon group As the reactive silicon group, the general formula (2): -SiR 2 3-a X a (2) (R 2 is independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or —OSi (R ′) 3 (R ′ Are each independently a triorganosiloxy group having 1 to 20 carbon atoms, and X is each independently a hydroxy group or a hydrolyzable group. A group represented by 1 to 3).
- the hydrolyzable group is not particularly limited as long as it is a conventionally known hydrolyzable group.
- Specific examples include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group.
- a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group are preferable. From the viewpoint that hydrolysis is mild and easy to handle.
- the group is particularly preferred.
- the hydrolyzable group or hydroxy group can be bonded to one silicon atom in the range of 1 to 3. When two or more hydrolyzable groups or hydroxy groups are bonded to the reactive silicon group, they may be the same or different.
- a in the general formula (1) and the general formula (2) is preferably 2 or 3 from the viewpoint of curability, and is particularly preferably 3 when quick curability is required. When stability is required, 2 is preferable.
- R 1 in the above general formula (1) is a divalent organic group having 1 to 20 carbon atoms containing at least one selected from the group consisting of hydrogen, oxygen and nitrogen as a constituent atom, for example, —CH 2 — , -C 2 H 4 -, - C 3 H 6 -, - C 4 H 8 -, - C 5 H 10 -, - C 6 H 4 -, - C 6 H 12 -, - CH (CH 3) - , —CH 2 —CH (CH 3 ) —, —CH 2 —CH (CH 3 ) —CH 2 —, —C 2 H 4 —CH (CH 3 ) —, —CH 2 —C 6 H 4 —, — Examples include CH 2 —C 6 H 4 —CH 2 —, —C 2 H 4 —C 6 H 4 — and the like.
- -CH 2 in terms of easy synthesis -, - CH 2 CH 2 - , - CH 2 CH
- R 2 in the general formula (1) include, for example, an alkyl group such as a methyl group and an ethyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, an aralkyl group such as a benzyl group, Examples thereof include a triorganosiloxy group, a chloromethyl group and a methoxymethyl group represented by —OSi (R ′) 3 in which R ′ is a methyl group, a phenyl group or the like. Of these, a methyl group is particularly preferred.
- the reactive silicon group include a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, and a diisopropoxymethylsilyl group.
- a trimethoxysilyl group, a triethoxysilyl group, and a dimethoxymethylsilyl group are more preferable, and a dimethoxymethylsilyl group is particularly preferable because of high activity and good curability.
- a dimethoxymethylsilyl group and a triethoxysilyl group are particularly preferable.
- triethoxysilyl group and diethoxymethylsilyl group are particularly preferable because the alcohol produced by the hydrolysis reaction of the reactive silicon group is ethanol and has higher safety.
- the introduction of the reactive silicon group may be performed by a known method. That is, for example, the following method is mentioned.
- An organic polymer having an unsaturated group by reacting an organic polymer having a functional group such as a hydroxy group in the molecule with an organic compound having an active group and an unsaturated group that are reactive with the functional group.
- a polymer is obtained.
- an unsaturated group-containing organic polymer is obtained by copolymerization with an unsaturated group-containing epoxy compound.
- the resulting reaction product is hydrosilylated by the action of a hydrosilane having a reactive silicon group.
- the method (I) or the method (III) in which the polymer having a hydroxyl group at the terminal is reacted with the compound having an isocyanate group and a reactive silicon group has a relatively short reaction time. It is preferable because a high conversion rate can be obtained. Furthermore, the organic polymer having a reactive silicon group obtained by the method (I) becomes a curable composition having a lower viscosity and better workability than the organic polymer obtained by the method (III).
- the organic polymer obtained by the method (II) has a strong odor based on mercaptosilane, and therefore the method (I) is particularly preferred.
- hydrosilane compound used in the method (I) include halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, and phenyldichlorosilane; trimethoxysilane, triethoxysilane, and methyldiethoxysilane.
- Alkoxysilanes such as methyldimethoxysilane, phenyldimethoxysilane, 1- [2- (trimethoxysilyl) ethyl] -1,1,3,3-tetramethyldisiloxane; methyldiacetoxysilane, phenyldiacetoxysilane Examples thereof include, but are not limited to, acyloxysilanes such as: ketoximate silanes such as bis (dimethylketoximate) methylsilane and bis (cyclohexylketoximate) methylsilane.
- halogenated silanes and alkoxysilanes are particularly preferable, and alkoxysilanes are particularly preferable because the hydrolyzability of the resulting curable composition is gentle and easy to handle.
- alkoxysilanes methyldimethoxysilane is preferred because it is easily available and the curable composition containing the resulting organic polymer has high curability, storage stability, elongation characteristics, and tensile strength. Trimethoxysilane is particularly preferable from the viewpoints of curability and restorability of the resulting curable composition.
- a compound having a mercapto group and a reactive silicon group is converted into an unsaturated bond site of an organic polymer by a radical addition reaction in the presence of a radical initiator and / or a radical generation source.
- a radical addition reaction in the presence of a radical initiator and / or a radical generation source.
- transducing etc. is mentioned, it does not specifically limit.
- Specific examples of the compound having a mercapto group and a reactive silicon group include, for example, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -mercaptopropylmethyldimethoxysilane, ⁇ -mercaptopropyltriethoxysilane, and ⁇ -mercaptopropylmethyldiethoxy. Examples include, but are not limited to, silane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, and the like.
- the method described in JP-A-3-47825 can be mentioned.
- the compound having an isocyanate group and a reactive silicon group include, for example, ⁇ -isocyanatopropyltrimethoxysilane, ⁇ -isocyanatopropylmethyldimethoxysilane, ⁇ -isocyanatopropyltriethoxysilane, and ⁇ -isocyanatopropylmethyldiethoxy.
- Examples include, but are not limited to, silane, isocyanate methyltrimethoxysilane, isocyanatemethyltriethoxysilane, isocyanatemethyldimethoxymethylsilane, and isocyanatemethyldiethoxymethylsilane.
- a method of reacting a polymer having an isocyanate group at the terminal with a compound having an amino group and a reactive silicon group in the synthesis method of (III) for example, the method disclosed in JP-A-2005-2115, etc.
- the compound having an amino group and a reactive silicon group include, for example, ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropylmethyldimethoxysilane, ⁇ - (2-aminoethyl).
- N-ethyl examples include, but are not limited to, -3-amino-isobutyltrimethoxysilane, N-ethyl-3-amino-isobutyltriethoxysilane, N-ethyl-3-amino-isobutyldimethoxymethylsilane, and the like.
- N-ethyl-3-amino-isobutyltrimethoxysilane is sold by Momentive Performance Materials under the product name Silquest A-Link15 Silane, which is suitable for adjusting component (A). Yes.
- a silane compound in which three hydrolyzable groups are bonded to one silicon atom such as trimethoxysilane may cause a disproportionation reaction.
- an unstable compound such as dimethoxysilane is produced, which may make handling difficult.
- disproportionation reaction does not proceed with ⁇ -mercaptopropyltrimethoxysilane or ⁇ -isocyanatopropyltrimethoxysilane.
- the synthesis method (II) or (III) may be used. preferable.
- a divalent hydrocarbon group having 2 to 8 carbon atoms is more preferable, and a divalent hydrocarbon group having 2 carbon atoms is particularly preferable, and m is an integer of 0 to 19. In terms of availability and cost, 1 is preferable), and the disproportionation reaction does not proceed. For this reason, when a group in which three hydrolyzable groups are bonded to one silicon atom is introduced by the synthesis method (I), a silane compound represented by the general formula (3) should be used. Is preferred.
- silane compound represented by the general formula (3) examples include 1- [2- (trimethoxysilyl) ethyl] -1,1,3,3-tetramethyldisiloxane, 1- [2- (trimethoxy Silyl) propyl] -1,1,3,3-tetramethyldisiloxane, 1- [2- (trimethoxysilyl) hexyl] -1,1,3,3-tetramethyldisiloxane.
- the organic polymer (A) and the organic polymer (B) having a reactive silicon group may be linear or branched. However, in order to better exhibit the effects of the present invention, the organic polymer (A) and the organic polymer (B) may be linear. It is desirable that The number average molecular weight of the component (A) is about 800 to 15,000, more preferably 1,000 to 13,000, and particularly preferably 2,000 to 11,000 in terms of polystyrene in GPC. When the number average molecular weight of the component (A) is less than 800, the effect of improving the contamination tends to be insufficient, and the cost is not preferable. On the other hand, if it exceeds 15,000, the viscosity tends to be inconvenient because of high viscosity.
- the number average molecular weight of the component (B) is about 5,000 to 50,000, more preferably about 8,000 to 30,000, particularly preferably 10,000 to 25, in the same measurement method as described above. 000.
- the number average molecular weight of the component (B) is less than 5,000, the elongation of the cured product is low and tends to be unsuitable as a building sealing material.
- it exceeds 30,000 the viscosity becomes high, the workability at a low temperature is particularly poor, and a problem called “threading” occurs when used as a sealing material for construction, which is not preferable.
- the number average molecular weight of the polymer contained in the curable composition is determined for each peak of the GPC chart.
- multiple types of initiators multiple types of polymers can be obtained by a single polymerization operation, but in that case, instead of calculating the number average molecular weight collectively, for each polymer, that is, for each peak The number average molecular weight is determined.
- the reactive silicon group contained in the organic polymer (A) can be used as a substitute for a normal plasticizer and does not cause a contamination problem. It is preferably present, and it is desirable that the number of components not containing a silicon group is as small as possible. That is, it is desirable that the number of reactive silicon groups contained in the organic polymer (A) is approximately one.
- the number of reactive silicon groups contained in the organic polymer (B) is desirably 1.2 to 5 on average in one molecule of the polymer, preferably 1.3 to 3, more preferably The number is preferably 1.4 to 2.
- the organic polymer (A) has a structure having a reactive silicon group only at one end of the organic polymer. It is a polymer in which a silicon group is introduced only at one end, and is characterized by a structural formula represented by the general formula (1) in order to increase the introduction rate of this silicon group. Therefore, the organic polymer (A) needs to take a synthetic method in which a silicon group is introduced only at one end as much as possible.
- an organic polymer having only one active hydrogen such as a hydroxyl group in one molecule is used as the organic polymer used in the section (I).
- an organic polymer having only one active hydrogen per molecule is used as an initiator in the production of the component (A) with an actual machine, when the amount of preparation is small and sufficient stirring is not ensured, 1
- a compound having two or more active hydrogens in the molecule may be used in combination. In such a case, on average, an organic polymer containing two reactive silicon groups is mixed in one molecule, but on average, the number of reactive silicon groups is less than one in one molecule. If adjusted, there is no particular problem.
- Examples of the initiator containing only one active hydrogen per molecule include the following compounds. That is, monovalent 1st grade, 2nd grade, 3rd grade alcohol such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol; monovalent such as allyl alcohol, methallyl alcohol, propenyl alcohol, etc.
- ethylene glycol diethylene glycol, propylene glycol, dipropylene glycol, 1, 3-propanediol, neopentyl glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6 -Monoallyl etherified product obtained by monoallyl etherification of hexanediol, 1, 4-cyclohexanediol, etc. or monovinyl etherified product obtained by monovinyl etherification Monovalent unsaturated group-containing alcohols such as monovalent ethers, and monovalent saturated alcohols such as monoalkyl etherified monoalkyl ethers described above, but are not limited thereto.
- alcohols are preferable from the viewpoint of reactivity and availability, and alcohols having 3 to 7 carbon atoms are most preferable. Alcohols having 1 or 2 carbon atoms have low boiling points and are not suitable as initiators because they are difficult to stabilize as liquids. On the other hand, in the case of an alcohol having 8 or more carbon atoms, the reactivity tends to decrease when a reactive silicon group is introduced into the obtained organic polymer. Of the alcohols, n-butanol is most preferred.
- a polyether polymer having a hydroxyl group only at one end is more convenient.
- a polymer having a molecular weight of about 1,000 to 5,000 can be used.
- Sanyo Kasei's polyoxypropylene monobutyl ether (trade name: Newpol) can be preferably used.
- an organic polymer having a high content of a component having one reactive silicon group in one molecule can be obtained.
- the reactive silicon group may be at the end of the main chain or the side chain of the organic polymer molecular chain, or at both ends.
- the reactive silicon group is only at the end of the main chain of the molecular chain, so that the strength and elongation are high.
- a rubber-like cured product having a low elastic modulus is easily obtained, which is preferable.
- the polyoxyalkylene polymer essentially has the general formula (4): -R 5 -O- (4)
- R 5 is a polymer having a repeating unit represented by a linear or branched alkylene group having 1 to 14 carbon atoms
- R 5 in the general formula (4) is 1 to 14 carbon atoms.
- 2 to 4 linear or branched alkylene groups are preferred.
- Specific examples of the repeating unit represented by the general formula (4) include -CH 2 O -, - CH 2 CH 2 O -, - CH 2 CH (CH 3) O -, - CH 2 CH (C 2 H 5) O -, - CH 2 C (CH 3) 2 O-, —CH 2 CH 2 CH 2 CH 2 O— Etc.
- the main chain skeleton of the polyoxyalkylene polymer may be composed of only one type of repeating unit, or may be composed of two or more types of repeating units.
- a polymer comprising a propylene oxide polymer as a main component is preferable because it is amorphous or has a relatively low viscosity.
- Examples of the method for synthesizing a polyoxyalkylene polymer include a polymerization method using an alkali catalyst such as KOH, and a complex obtained by reacting an organoaluminum compound with porphyrin as disclosed in JP-A-61-215623.
- Polymerization method using transition metal compound-porphyrin complex catalyst Japanese Patent Publication No. 46-27250, Japanese Patent Publication No. 59-15336, US Pat. No. 3,278,457, US Pat. No. 3,278,458, US Pat. No. 3,278,459, US Pat. No. 3,427,256, US Pat. No. 3,427,334, Polymerization method using double metal cyanide complex catalyst as shown in US Pat. No.
- Polyoxy having a number average molecular weight of 6,000 or more, a high molecular weight of Mw / Mn of 1.6 or less, and a narrow molecular weight distribution Alkylene polymer can be exemplified, but not particularly limited thereto.
- the above polyoxyalkylene polymers having a reactive silicon group may be used alone or in combination of two or more.
- the saturated hydrocarbon polymer is a polymer that does not substantially contain a carbon-carbon unsaturated bond other than an aromatic ring, and the polymer constituting the skeleton thereof is (1) ethylene, propylene, 1-butene, isobutylene, etc.
- the main monomer is an olefin compound having 2 to 6 carbon atoms, or (2) a diene compound such as butadiene or isoprene is homopolymerized, or is copolymerized with the olefin compound. After that, it can be obtained by a method such as hydrogenation.
- the isobutylene polymer and the hydrogenated polybutadiene polymer can easily introduce a functional group at the terminal, easily control the molecular weight, The number can be increased, and an isobutylene polymer is particularly preferable.
- Those whose main chain skeleton is a saturated hydrocarbon polymer have characteristics of excellent heat resistance, weather resistance, durability, and moisture barrier properties.
- all of the monomer units may be formed from isobutylene units, or may be a copolymer with other monomers, but the repeating unit derived from isobutylene is 50 from the viewpoint of rubber properties.
- Those containing not less than wt% are preferred, those containing not less than 80 wt% are more preferred, and those containing 90 to 99 wt% are particularly preferred.
- Examples of the method for producing a saturated hydrocarbon polymer having a reactive silicon group include, for example, JP-B-4-69659, JP-B-7-108928, JP-A-63-254149, JP-A-64-22904, Although described in each specification of Kaihei 1-197509, Japanese Patent Publication No. 2539445, Japanese Patent Publication No. 2873395, and Japanese Patent Application Laid-Open No. 7-53882, it is not particularly limited thereto.
- the saturated hydrocarbon polymer having a reactive silicon group may be used alone or in combination of two or more.
- the (meth) acrylic acid ester monomer constituting the main chain of the (meth) acrylic acid ester polymer is not particularly limited, and various types can be used. Examples include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, N-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth)
- the following vinyl monomers can be copolymerized together with the (meth) acrylic acid ester monomer.
- the vinyl monomer include styrene monomers such as styrene, vinyl toluene, ⁇ -methyl styrene, chlorostyrene, styrene sulfonic acid and salts thereof; silicon-containing vinyl monomers such as vinyl trimethoxysilane and vinyl triethoxysilane; Maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid, monoalkyl and dialkyl esters of fumaric acid; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, Maleimide monomers such as dodecylmaleimide, stearylmaleimide, pheny
- the polymer which consists of a styrene-type monomer and a (meth) acrylic-acid type monomer from the physical property of a product etc. is preferable. More preferred is a (meth) acrylic polymer comprising an acrylate monomer and a methacrylic acid ester monomer, and particularly preferred is an acrylic polymer comprising an acrylate monomer.
- a butyl acrylate monomer is more preferred from the viewpoint that physical properties such as low viscosity of the blend, low modulus of the cured product, high elongation, weather resistance, and heat resistance are required.
- copolymers based on ethyl acrylate are more preferred.
- This polymer mainly composed of ethyl acrylate is excellent in oil resistance but tends to be slightly inferior in low temperature characteristics (cold resistance). Therefore, in order to improve the low temperature characteristics, a part of ethyl acrylate is converted into butyl acrylate. It is also possible to replace it.
- the ratio of butyl acrylate is increased, its good oil resistance is impaired. Therefore, for applications requiring oil resistance, the ratio is preferably 40% or less, and more preferably 30% or less. More preferably.
- the ratio is preferably 40% or less. In accordance with various uses and required purposes, it is possible to obtain suitable polymers by changing the ratio in consideration of required physical properties such as oil resistance, heat resistance and low temperature characteristics.
- examples of excellent balance of physical properties such as oil resistance, heat resistance, and low temperature characteristics include ethyl acrylate / butyl acrylate / 2-methoxyethyl acrylate (by weight ratio of 40-50 / 20- 30/30 to 20).
- these preferred monomers may be copolymerized with other monomers, and further block copolymerized, and in that case, these preferred monomers are preferably contained in a weight ratio of 40% or more.
- (meth) acrylic acid represents acrylic acid and / or methacrylic acid.
- the method for synthesizing the (meth) acrylic acid ester-based polymer is not particularly limited, and may be performed by a known method.
- a polymer obtained by a normal free radical polymerization method using an azo compound or a peroxide as a polymerization initiator has a problem that the molecular weight distribution is generally as large as 2 or more and the viscosity is increased. Yes. Therefore, in order to obtain a (meth) acrylate polymer having a narrow molecular weight distribution and a low viscosity and having a crosslinkable functional group at the molecular chain terminal at a high ratio. It is preferable to use a living radical polymerization method.
- the “atom transfer radical polymerization method” for polymerizing a (meth) acrylate monomer using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst In addition to the characteristics of the “living radical polymerization method”, it has a halogen or the like that is relatively advantageous for functional group conversion reaction, and has a specific functional group because it has a large degree of freedom in designing initiators and catalysts ( The method for producing a (meth) acrylic acid ester polymer is more preferable. Examples of this atom transfer radical polymerization method include Matyjazewski et al., Journal of American Chemical Society (J. Am. Chem. Soc.) 1995, 117, 5614.
- Examples of the method for producing a (meth) acrylic acid ester-based polymer having a reactive silicon group include chain transfer described in JP-B-3-14068, JP-B-4-55444, JP-A-6-211922, and the like.
- a production method using a free radical polymerization method using an agent is disclosed.
- Japanese Patent Application Laid-Open No. 9-272714 discloses a production method using an atom transfer radical polymerization method, but is not particularly limited thereto.
- the (meth) acrylic acid ester-based polymer having a reactive silicon group may be used alone or in combination of two or more.
- organic polymers having a reactive silicon group may be used alone or in combination of two or more.
- a group consisting of a polyoxyalkylene polymer having a reactive silicon group, a saturated hydrocarbon polymer having a reactive silicon group, and a (meth) acrylic acid ester polymer having a reactive silicon group An organic polymer obtained by blending two or more selected from the above can also be used.
- a method for producing an organic polymer obtained by blending a polyoxyalkylene polymer having a reactive silicon group and a (meth) acrylic acid ester polymer having a reactive silicon group is disclosed in JP-A-59-122541.
- Japanese Laid-Open Patent Publication No. 63-112642 Japanese Laid-Open Patent Publication No. 6-172631, and Japanese Laid-Open Patent Publication No. 11-116763, the invention is not particularly limited thereto.
- a preferred specific example has a reactive silicon group and a molecular chain substantially having the following general formula (5): —CH 2 —C (R 6 ) (COOR 7 ) — (5) (Meth) acrylic acid ester monomer unit having an alkyl group having 1 to 8 carbon atoms represented by (R 6 is a hydrogen atom or a methyl group, R 7 is an alkyl group having 1 to 8 carbon atoms) And the following general formula (6): —CH 2 —C (R 6 ) (COOR 8 ) — (6) (R 6 is the same as above, R 8 represents an alkyl group having 9 or more carbon atoms) and is a copolymer consisting of a (meth) acrylic acid ester monomer unit having an alkyl group having 9 or more carbon atoms In this method, a polyoxyalkylene polymer having a reactive silicon group is blended with the polymer.
- R 7 in the general formula (5) is, for example, 1 to 8, preferably 1 to 1 carbon atoms such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group, and a 2-ethylhexyl group. 4, more preferably 1 or 2 alkyl groups.
- the alkyl group R 7 may alone, or may be a mixture of two or more.
- R 8 in the general formula (6) is, for example, 9 or more carbon atoms such as a nonyl group, a decyl group, a lauryl group, a tridecyl group, a cetyl group, a stearyl group, or a behenyl group, usually 10 to 30, preferably Examples include 10 to 20 long-chain alkyl groups.
- the alkyl group of R 8 is similar to the case of R 7, individually may or may be a mixture of two or more.
- the molecular chain of the (meth) acrylic acid ester polymer is substantially composed of monomer units represented by the general formula (5) and the general formula (6). It means that the total of the monomer units of the general formula (5) and the general formula (6) present in the coal exceeds 50% by weight.
- the total of the monomer units of general formula (5) and general formula (6) is preferably 70% by weight or more.
- the abundance ratio of the monomer unit of the general formula (5) and the monomer unit of the general formula (6) is preferably 95: 5 to 40:60, and more preferably 90:10 to 60:40. preferable.
- Examples of monomer units other than the general formula (5) and general formula (6) that may be contained in the copolymer include acrylic acid such as acrylic acid and methacrylic acid; acrylamide, methacrylamide, N- Monomers containing amide groups such as methylol acrylamide and N-methylol methacrylamide, epoxy groups such as glycidyl acrylate and glycidyl methacrylate, and amino groups such as diethylaminoethyl acrylate, diethylaminoethyl methacrylate and aminoethyl vinyl ether; other acrylonitrile, styrene, ⁇ -Monomer units derived from methyl styrene, alkyl vinyl ether, vinyl chloride, vinyl acetate, vinyl propionate, ethylene and the like.
- a method for producing an organic polymer obtained by blending a (meth) acrylic acid ester-based polymer having a reactive silicon functional group, in the presence of an organic polymer having a reactive silicon group (A method of polymerizing a meth) acrylate monomer can be used. This production method is specifically disclosed in JP-A-59-78223, JP-A-59-168014, JP-A-60-228516, JP-A-60-228517, etc. It is not limited to these.
- the main chain skeleton of the organic polymer may contain other components such as a urethane bond component as long as the effects of the present invention are not significantly impaired.
- the urethane bond component is not particularly limited, and examples thereof include a group (hereinafter also referred to as an amide segment) generated by a reaction between an isocyanate group and an active hydrogen group.
- the amide segment has the general formula (7): —NR 9 —C ( ⁇ O) — (7) (R 9 represents an organic group or a hydrogen atom).
- the amide segment is a urethane group formed by a reaction between an isocyanate group and a hydroxy group; a urea group formed by a reaction between an isocyanate group and an amino group; and formed by a reaction between an isocyanate group and a mercapto group.
- a thiourethane group etc. can be mentioned.
- groups generated by the reaction of the active hydrogen in the urethane group, urea group, and thiourethane group with an isocyanate group are also included in the group of the general formula (7).
- An example of an industrially easy production method of an organic polymer having an amide segment and a reactive silicon group is as follows.
- An organic polymer having an active hydrogen-containing group at the terminal is reacted with an excess polyisocyanate compound to produce a polyurethane-based main polymer.
- all or a part of the isocyanate group is represented by the general formula (8): W—R 10 —SiR 2 3-a X a (8) (R 2 , X and a are the same as above.
- R 10 is a divalent organic group, more preferably a hydrocarbon group having 1 to 20 carbon atoms.
- W is a hydroxy group, a carboxy group, a mercapto group and Examples thereof include those produced by a method in which a W group of a silicon compound represented by an amino group (an active hydrogen-containing group selected from primary or secondary) is reacted.
- Examples of known production methods of organic polymers related to this production method include Japanese Patent Publication No. 46-12154 (US Pat. No. 3,632,557), Japanese Patent Application Laid-Open No. 58-109529 (US Pat. No. 4,374,237), Japanese Patent Application Laid-Open No. Sho 62. No. 13430 (US Pat. No.
- JP-A-8-53528 EP0676403
- JP-A-10-204144 EP0831108
- JP-T 2003-508561 US Pat. No. 6,1979,912
- JP-A-6-21879 US) No. 5364955
- JP-A-10-53637 US Pat. No. 5,757,751
- JP-A-11-100197 JP-A-2000-169544
- JP-A-2000-169545 JP-A-2002-212415
- JP-A-3313360 JP-A-3313360.
- Examples of known production methods for organic polymers related to this production method include JP-A-11-279249 (US Pat. No. 5,990,257), JP-A 2000-119365 (US Pat. No. 6,046,270), JP-A 58- No. 29818 (US Pat. No. 4,345,053), JP-A-3-47825 (US Pat. No. 5,068,304), JP-A-11-60724, JP-A-2002-155138, JP-A-2002-249538, WO03 / 018658, WO03 / 059981 Etc.
- organic polymer having an active hydrogen-containing group at the terminal examples include an oxyalkylene polymer having a hydroxy group at the terminal (polyether polyol), a polyacryl polyol, a polyester polyol, and a saturated hydrocarbon polymer having a hydroxy group at the terminal (Polyolefin polyol), polythiol compounds, polyamine compounds and the like.
- polyether polyol, polyacryl polyol, and polyolefin polyol are preferable because the obtained organic polymer has a relatively low glass transition temperature and the resulting cured product is excellent in cold resistance.
- polyether polyols are particularly preferred because the resulting organic polymer has a low viscosity, good workability, and good deep part curability and adhesiveness.
- Polyacryl polyols and saturated hydrocarbon polymers are more preferred because the resulting cured organic polymer has good weather resistance and heat resistance.
- polyether polyol those produced by any production method can be used, but those having at least 0.7 hydroxy groups per molecular terminal in terms of the total molecular average are preferable.
- an oxyalkylene polymer produced using a conventional alkali metal catalyst, an initiator such as a polyhydroxy compound having at least two hydroxy groups in the presence of a double metal cyanide complex or cesium an alkylene Examples include oxyalkylene polymers produced by reacting oxides.
- a polymerization method using a double metal cyanide complex has a lower degree of unsaturation, a smaller Mw / Mn, a lower viscosity, a high acid resistance, and a high weather resistance oxyalkylene heavy. It is preferable because a coalescence can be obtained.
- polyacrylic polyol examples include a polyol having a (meth) acrylic acid alkyl ester (co) polymer as a skeleton and a hydroxy group in the molecule.
- the polymer synthesis method is preferably a living radical polymerization method and more preferably an atom transfer radical polymerization method because the molecular weight distribution is narrow and viscosity can be lowered.
- Specific examples include Alfon UH-2000 manufactured by Toagosei Co., Ltd.
- polyisocyanate compound examples include aromatic polyisocyanates such as toluene (tolylene) diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate; aliphatic polyisocyanates such as isophorone diisocyanate and hexamethylene diisocyanate. .
- the silicon compound of the general formula (8) is not particularly limited, but specific examples include ⁇ -aminopropyltrimethoxysilane, N- ( ⁇ -aminoethyl) - ⁇ -aminopropyltrimethoxysilane, (N— Amino such as phenyl) - ⁇ -aminopropyltrimethoxysilane, N-ethylaminoisobutyltrimethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane Group-containing silanes; hydroxy group-containing silanes such as ⁇ -hydroxypropyltrimethoxysilane; mercapto group-containing silanes such as ⁇ -mercaptopropyltrimethoxysilane; and the like.
- JP-A-6-2111879 (US Pat. No. 5,364,955), JP-A-10-53637 (US Pat. No. 5,757,751), JP-A-10-204144 (EP0831108), JP-A 2000-169544, JP-A 2000-169545.
- Michael addition reaction products of various ⁇ , ⁇ -unsaturated carbonyl compounds and primary amino group-containing silanes, or various (meth) acryloyl group-containing silanes and primary amino group-containing compounds can also be used as the silicon compound of general formula (8).
- the reactive silicon group-containing isocyanate compound of the general formula (9) is not particularly limited, but specific examples include ⁇ -trimethoxysilylpropyl isocyanate, ⁇ -triethoxysilylpropyl isocyanate, ⁇ -methyldimethoxysilylpropyl isocyanate. ⁇ -methyldiethoxysilylpropyl isocyanate, trimethoxysilylmethyl isocyanate, triethoxymethylsilylmethyl isocyanate, dimethoxymethylsilylmethyl isocyanate, diethoxymethylsilylmethyl isocyanate and the like. Further, as described in JP-A No. 2000-119365 (US Pat. No. 6,046,270), a compound obtained by reacting a silicon compound of the general formula (8) with an excess of the polyisocyanate compound is also represented by the general formula: It can be used as the reactive silicon group-containing isocyanate compound (9).
- the organic polymer obtained by the above method has the general formula (10) in the main chain skeleton: —NR 11 —C ( ⁇ O) — (10) (R 11 represents a hydrogen atom or a substituted or unsubstituted organic group). Since this structure has a relatively high polarity, it tends to increase the strength of the cured product and the adhesion to the substrate, which is desirable.
- the amount of component (B) used is preferably about 20 to 2000 parts by weight, more preferably about 100 to 1000 parts by weight, and particularly preferably about 120 to 700 parts by weight per 100 parts by weight of component (A).
- component (B) is less than this range, the cured product becomes too soft, and sufficient strength necessary for a sealing material or an adhesive cannot be obtained.
- component (B) exceeds this range, the workability of the curable composition is deteriorated and the modulus of the cured product is increased.
- a silanol condensation catalyst is used.
- an organic tin-based curing catalyst can be given.
- the organic tin catalyst include dimethyltin diacetate, dimethyltin bis (acetylacetonate), dibutyltin dilaurate, dibutyltin maleate, dibutyltin phthalate, dibutyltin dioctanoate, dibutyltin bis (2-ethylhexanoate) ), Dibutyltin bis (methyl maleate), dibutyltin bis (ethyl maleate), dibutyltin bis (butylmaleate), dibutyltin bis (octylmaleate), dibutyltin bis (tridecylmaleate), dibutyltin Bis (benzyl maleate), dibutyl tin diacetate, dioctyl tin bis (
- a curing catalyst other than the above-described organotin type can also be used.
- Specific examples thereof include titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, titanium tetrakis (acetylacetonate), bis (acetylacetonato) diisopropoxytitanium, diisopropoxytitanium bis (ethylacetocetate); aluminum tris And organic aluminum compounds such as (acetylacetonate), aluminum tris (ethylacetoacetate), diisopropoxyaluminum ethylacetoacetate; and zirconium compounds such as zirconium tetrakis (acetylacetonate).
- carboxylic acid and / or carboxylic acid metal salt can also be used as a curing catalyst.
- an amidine compound as described in WO2008 / 078654 can also be used.
- amidine compounds include 1- (o-tolyl) biguanide, 1-phenylguanidine, 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, 1,5,7-triazabicyclo [4.4. .0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] dec-5-ene, and the like, but are not limited thereto.
- the curing catalyst is used in an amount of 0.1 to 10 parts by weight, preferably 0.2 to 8 parts by weight, more preferably 0.3 to 100 parts by weight of the total of component (A) and component (B). 2 parts by weight. If the amount is less than 0.1 parts by weight, the appropriate curability is not exhibited, and if the amount exceeds 10 parts by weight, the curing is too fast to form an appropriate cured product and the desired performance cannot be sufficiently exhibited.
- plasticizer may be used.
- plasticizers include non-aromatic dibasic acid esters such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate, diisodecyl succinate; aliphatic esters such as butyl oleate and methyl acetyl ricinoleate; Phosphate esters such as zil phosphate and tributyl phosphate; trimellitic acid esters; chlorinated paraffins; hydrocarbon oils such as alkyldiphenyl and partially hydrogenated terphenyl; process oils; epoxidized soybean oil, epoxy stearin And epoxy plasticizers such as benzyl acid.
- non-aromatic dibasic acid esters such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate, diisodecyl succinate
- aliphatic esters such as butyl oleate and
- Phthalate esters such as diisoundecyl phthalate and bisbutylbenzyl phthalate can also be used. However, in consideration of the influence on the human body and the environment, it is preferable to use less of these, and not to use them.
- the cyclohexane dicarboxylate obtained by water-adding said phthalic acid ester can be used without worrying about safety.
- This plasticizer is sold by BASF under the trade name Hexamol DINCH and can be easily obtained.
- the amount of low molecular weight plasticizer such as a phthalate ester plasticizer used is 200 parts by weight with respect to 100 parts by weight of the total of component (A) and component (B). The following is preferable, 100 parts by weight or less is preferable, and 50 parts by weight or less is preferable.
- a phthalate ester plasticizer When applying a paint on the curable composition, it is preferable to use a phthalate ester plasticizer in combination as long as the contamination is not lowered. It is because the adhesiveness of a coating film improves and the problem of peeling can be improved by using together. Specifically, it is preferably 1 to 20 parts by weight, more preferably 2 to 15 parts by weight, and most preferably 3 to 10 parts by weight with respect to 100 parts by weight of the total of component (A) and component (B).
- a polymeric plasticizer can be used for this curable composition.
- a high-molecular plasticizer is used, the initial physical properties are maintained over a long period of time as compared with the case where a low-molecular plasticizer that is a plasticizer containing no polymer component in the molecule is used.
- the drying property also referred to as paintability
- an alkyd paint is applied to the cured product can be improved.
- polymer plasticizer examples include vinyl polymers obtained by polymerizing vinyl monomers by various methods; esters of polyalkylene glycols such as diethylene glycol dibenzoate, triethylene glycol dibenzoate, and pentaerythritol ester; Polyester plasticizers obtained from dibasic acids such as sebacic acid, adipic acid, azelaic acid and phthalic acid and dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and dipropylene glycol; Is a polyether polyol such as 1,000 or more polyethylene glycol, polypropylene glycol, polytetramethylene glycol or the like.
- Polyethers such as derivatives converted to ether groups; polystyrenes such as polystyrene and poly- ⁇ -methylstyrene; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene, and the like. It is not a thing.
- polyethers and vinyl polymers are preferable.
- polyethers are used as a plasticizer, the surface curability and deep part curability are improved, and the curing delay after storage does not occur.
- Polypropylene glycol is more preferred.
- a vinyl polymer is preferable from the viewpoint of compatibility, weather resistance, and heat resistance.
- acrylic polymers and / or methacrylic polymers are preferred, and acrylic polymers such as polyacrylic acid alkyl esters are more preferred.
- the polymer synthesis method is preferably a living radical polymerization method and more preferably an atom transfer radical polymerization method because the molecular weight distribution is narrow and viscosity can be lowered.
- a polymer obtained by so-called SGO process obtained by continuous bulk polymerization of an alkyl acrylate monomer described in JP-A-2001-207157 at high temperature and high pressure.
- This plasticizer is sold by Toagosei Co., Ltd. under the trade name Alfon.
- the number average molecular weight of the polymer plasticizer is preferably 500 to 15,000, more preferably 800 to 10,000, still more preferably 1,000 to 8,000, and particularly preferably 1,000. 5,000. Most preferably, it is 1,000 to 3,000. If the molecular weight is too low, the plasticizer will flow out over time due to heat and rain, the initial physical properties cannot be maintained over a long period of time, and the alkyd paintability cannot be improved. Moreover, when molecular weight is too high, a viscosity will become high and workability
- the molecular weight distribution of the polymer plasticizer is not particularly limited, but is preferably narrow and is preferably less than 1.80. 1.70 or less is more preferable, 1.60 or less is more preferable, 1.50 or less is more preferable, 1.40 or less is particularly preferable, and 1.30 or less is most preferable.
- the number average molecular weight is measured by a GPC method in the case of a vinyl polymer, and by a terminal group analysis method in the case of a polyether polymer. Moreover, it is measured by molecular weight distribution (Mw / Mn) GPC method (polystyrene conversion).
- Plasticizers may be used alone or in combination of two or more. Further, a low molecular plasticizer and a high molecular plasticizer may be used in combination. These plasticizers can also be blended at the time of polymer production.
- the amount of the high molecular weight plasticizer used is 5 to 150 parts by weight, preferably 10 to 120 parts by weight, more preferably 20 to 100 parts by weight, based on 100 parts by weight of the total of the components (A) and (B). . If it is less than 5 parts by weight, the effect as a plasticizer will not be exhibited, and if it exceeds 150 parts by weight, the mechanical strength of the cured product will be insufficient.
- thermally expandable fine particle hollow body described in JP-A No. 2004-51701 or JP-A No. 2004-66749 can be used.
- the thermally expandable fine hollow body is a polymer outer shell material (vinylidene chloride copolymer, acrylonitrile copolymer, or vinylidene chloride-acrylonitrile copolymer weight) such as a hydrocarbon having 1 to 5 carbon atoms. It is a plastic sphere wrapped in a spherical shape.
- the gas pressure in the shell of the thermally expandable fine hollow body increases, and the volume of the polymer outer shell material softens, so that the volume expands dramatically and the bonding interface is Plays the role of peeling.
- By adding the thermally expandable fine hollow body it is possible to obtain an adhesive composition that can be easily peeled off without destroying the material simply by heating when not necessary, and can be peeled off without using any organic solvent.
- Aminosilane can be added to the curable composition of the present invention.
- Aminosilane is a compound having a reactive silicon group and amino group in the molecule, and is usually referred to as an adhesion-imparting agent.
- various adherends that is, inorganic substrates such as glass, aluminum, stainless steel, zinc, copper, and mortar, and organic substrates such as vinyl chloride, acrylic, polyester, polyethylene, polypropylene, polycarbonate, etc. When used, it exhibits a significant adhesive improvement effect under non-primer conditions or primer treatment conditions. When used under non-primer conditions, the effect of improving adhesion to various adherends is particularly remarkable.
- it is a compound that can function as a physical property modifier, an inorganic filler dispersibility improver, and the like.
- the reactive silicon group of aminosilane include the groups already exemplified, but methoxy group, ethoxy group and the like are preferable from the viewpoint of hydrolysis rate.
- the number of hydrolyzable groups is preferably 2 or more, particularly 3 or more.
- aminosilane examples include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyltriisopropoxysilane, ⁇ -aminopropylmethyldimethoxysilane, ⁇ -aminopropylmethyldiethoxysilane, ⁇ -(2-aminoethyl) aminopropyltrimethoxysilane, ⁇ - (2-aminoethyl) aminopropylmethyldimethoxysilane, ⁇ - (2-aminoethyl) aminopropyltriethoxysilane, ⁇ - (2-aminoethyl) amino Propylmethyldiethoxysilane, ⁇ - (2-aminoethyl) aminopropyltriisopropoxysilane, ⁇ - (2- (2-aminoethyl) aminoethyl) aminopropyltrimethoxysilane,
- ⁇ -aminopropyltrimethoxysilane, ⁇ - (2-aminoethyl) aminopropyltrimethoxysilane, and ⁇ - (2-aminoethyl) aminopropylmethyldimethoxysilane are used. preferable. Only one type of aminosilane may be used, or two or more types may be used in combination. It has been pointed out that ⁇ - (2-aminoethyl) aminopropyltrimethoxysilane is irritating compared to other aminosilanes, and instead of reducing this aminosilane, ⁇ -aminopropyltrimethoxysilane should be used in combination. Can alleviate irritation.
- the compounding amount of aminosilane is preferably about 1 to 10 parts by weight, more preferably 2 to 5 parts by weight, with respect to 100 parts by weight of the total of component (A) and component (B). If the amount of aminosilane is less than 1 part by weight, sufficient adhesion may not be obtained. On the other hand, if the blending amount exceeds 10 parts by weight, the cured product becomes brittle and sufficient strength cannot be obtained, and the curing rate may be slow.
- an adhesion-imparting agent other than aminosilane can be used.
- adhesion-imparting agents other than aminosilane include ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycidoxypropylmethyldimethoxysilane, ⁇ - (3,4-epoxy Epoxy group-containing silanes such as cyclohexyl) ethyltrimethoxysilane and ⁇ - (3,4-epoxycyclohexyl) ethyltriethoxysilane; ⁇ -isocyanatopropyltrimethoxysilane, ⁇ -isocyanatopropyltriethoxysilane, ⁇ -isocyanatopropylmethyl Isocyanate group-containing silanes such as diethoxysilane, ⁇ -isocyanatopropylmethyldimethoxysilane, (isocyanatemethyl) trimethoxysilane, (isocyanatemethyl)
- the condensate which condensed the said silane partially can also be used.
- amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, silylated polyesters, etc., which are derivatives of these, can also be used as silane coupling agents.
- the silane coupling agent used in the present invention is used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the total of the components (A) and (B). In particular, it is preferably used in the range of 0.5 to 5 parts by weight.
- the effects of the silane coupling agent added to the curable composition of the present invention include various adherends, that is, inorganic substrates such as glass, aluminum, stainless steel, zinc, copper, and mortar, vinyl chloride, acrylic, and polyester. When used on organic substrates such as polyethylene, polypropylene, polycarbonate, etc., it exhibits a remarkable adhesive improvement effect under non-primer conditions or primer treatment conditions. When used under non-primer conditions, the effect of improving adhesion to various adherends is particularly remarkable.
- Specific examples other than the silane coupling agent are not particularly limited, and examples thereof include epoxy resins, phenol resins, sulfur, alkyl titanates, and aromatic polyisocyanates.
- the adhesiveness-imparting agent may be used alone or in combination of two or more. By adding these adhesion-imparting agents, the adhesion to the adherend can be improved.
- ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, and ⁇ -glycidoxypropylmethyldimethoxysilane are preferred in order to ensure good adhesion.
- the amount of the adhesion-imparting agent used is preferably about 0.01 to 10 parts by weight, more preferably about 0.1 to 5 parts by weight, based on 100 parts by weight of the total of the components (A) and (B). A weight of about 1 to 3 parts is particularly preferred. If the blending amount of the adhesiveness-imparting agent is below this range, sufficient adhesion may not be obtained. On the other hand, if the blending amount of the adhesion-imparting agent exceeds this range, practical deep curability may not be obtained.
- the adhesiveness imparting agent in addition to the adhesiveness imparting agent, is not particularly limited.
- epoxy resin, phenol resin, sulfur, alkyl titanates, aromatic polyisocyanate and the like can be used.
- the adhesiveness-imparting agent may be used alone or in combination of two or more.
- the epoxy resin may lower the catalytic activity depending on the addition amount, it is preferable that the addition amount of the epoxy resin is small in the curable composition of the present invention.
- the amount of the epoxy resin used is preferably 5 parts by weight or less, more preferably 0.5 parts by weight or less, and substantially not contained with respect to 100 parts by weight of the total of the components (A) and (B). It is particularly preferred.
- antioxidant antioxidant
- antioxidant antioxidant
- cured material can be improved.
- antioxidant include hindered phenols, monophenols, bisphenols, and polyphenols, with hindered phenols being particularly preferred.
- Tinuvin 622LD, Tinuvin 144, CHIMASSORB 944LD, CHIMASSORB 119FL (all of which are manufactured by BASF Japan Ltd.); MARK LA-57, MARK LA-62, MARK LA-67, MARK LA-63, MARK LA-68 (all above Also manufactured by ADEKA Corporation); Sanol LS-770, Sanol LS-765, Sanol LS-292, Sanol LS-2626, Sanol LS-1114, Sanol LS-744 (all of which are manufactured by Sankyo Lifetech Co., Ltd.) A hindered amine light stabilizer can also be used.
- the amount of the antioxidant used is preferably in the range of 0.1 to 5 parts by weight, more preferably 0.2 to 3 parts by weight based on 100 parts by weight of the total of the components (A) and (B). Part.
- a light stabilizer can be used in the composition obtained in the present invention.
- Use of a light stabilizer can prevent photooxidation degradation of the cured product.
- the light stabilizer include benzotriazole, hindered amine, and benzoate compounds, with hindered amines being particularly preferred.
- the light stabilizer may be used in an amount of 0.1 to 5 parts by weight, more preferably 0.2 to 3 parts by weight, based on 100 parts by weight of the total amount of the components (A) and (B). Part. Specific examples of the light stabilizer are also described in JP-A-9-194731.
- a tertiary amine is used as a hindered amine light stabilizer as described in JP-A-5-70531. It is preferable to use a contained hindered amine light stabilizer for improving the storage stability of the composition.
- Tinuvin 622LD Tinuvin 144, CHIMASSORB 119FL (all of these are manufactured by BASF Japan Ltd.); MARK LA-57, LA-62, LA-67, LA-63 (all of which are stocks)
- light stabilizers such as SANOL LS-765, LS-292, LS-2626, LS-1114, and LS-744 (all of which are manufactured by BASF Japan Ltd.).
- an ultraviolet absorber can be used.
- the surface weather resistance of the cured product can be enhanced.
- ultraviolet absorbers include benzophenone-based, benzotriazole-based, salicylate-based, substituted tolyl-based, and metal chelate-based compounds, and benzotriazole-based compounds are particularly preferable.
- the amount of the ultraviolet absorber used is preferably in the range of 0.1 to 5 parts by weight, more preferably 0.2 to 3 parts by weight, with respect to 100 parts by weight of the total of the components (A) and (B). Part. It is preferable to use a phenolic or hindered phenolic antioxidant, a hindered amine light stabilizer and a benzotriazole ultraviolet absorber in combination.
- a filler can be added to the composition of the present invention.
- Fillers include reinforcing silica such as fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrous silicic acid, and carbon black; heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate Diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, aluminum fine powder, flint powder, zinc oxide, activated zinc white, shirasu balloon, glass microballoon, phenolic resin and vinylidene chloride Examples thereof include fillers such as resin powders such as resin organic microballoons, PVC powder, and PMMA powders; and fibrous fillers such as glass fibers and filaments.
- the amount used is 1 to 150 parts by weight, preferably 10 to 100 parts by weight, based on 100 parts by weight of the total of component (A) and
- fillers mainly fume silica, precipitated silica, crystalline silica, fused silica, dolomite, silicic anhydride, hydrous silicic acid and carbon black, surface treatment fine
- a filler selected from calcium carbonate, calcined clay, clay, activated zinc white and the like is preferable, and it is preferable to use it in a range of 1 to 100 parts by weight with respect to 100 parts by weight of the total of component (A) and component (B). Results are obtained.
- calcium carbonate such as titanium oxide and heavy calcium carbonate, magnesium carbonate, talc, ferric oxide, zinc oxide, and shirasu balloon
- a filler selected from the above is used in a range of 5 to 100 parts by weight with respect to a total of 100 parts by weight of the component (A) and the component (B)
- preferable results are obtained.
- calcium carbonate has a greater effect of improving the breaking strength, breaking elongation, and adhesiveness of the cured product as the value of the specific surface area increases.
- these fillers may be used alone or in combination of two or more.
- the particle diameter of the surface-treated fine calcium carbonate is preferably 0.5 ⁇ m or less, and the surface treatment is preferably treated with a fatty acid or a fatty acid salt. Moreover, the particle size of calcium carbonate having a large particle size is preferably 1 ⁇ m or more, and an untreated surface can be used.
- an organic balloon or an inorganic balloon In order to improve the workability (such as sharpness) of the composition and to make the surface of the cured product matt, it is preferable to add an organic balloon or an inorganic balloon. These fillers can be surface-treated, and may be used alone or in combination of two or more. In order to improve workability (such as sharpness), the balloon particle size is preferably 0.1 mm or less. In order to make the surface of the cured product matt, 5 to 300 ⁇ m is preferable.
- the composition of the present invention is an adhesive for exterior wall joints, exterior tiles, and exterior wall tiles such as siding boards, particularly ceramic siding boards, because of the good chemical resistance of the cured product.
- high-quality outer walls are used as outer walls due to the mixture of spatter coating, colored aggregates, and the like.
- the composition of the present invention is blended with a scaly or granular substance having a diameter of 0.1 mm or more, preferably about 0.1 to 5.0 mm, the cured product is in harmony with such a high-quality outer wall.
- the chemical resistance is excellent, the appearance of the cured product is an excellent composition that lasts for a long time.
- the surface becomes sandy or sandstone-like rough, and when a scaly material is used, the surface becomes uneven.
- preferred diameters, blending amounts, materials, etc. of the scaly or granular substance are as follows.
- the diameter is 0.1 mm or more, preferably about 0.1 to 5.0 mm, and those having an appropriate size are used according to the material and pattern of the outer wall.
- the thing of about 0.2 mm to 5.0 mm and about 0.5 mm to 5.0 mm can also be used.
- the thickness is about 1/10 to 1/5 of the diameter (about 0.01 to 1.00 mm).
- the scale-like or granular substance is mixed in advance in the main sealing material and transported to the construction site as a sealing material, or mixed in the main sealing material at the construction site when used.
- the scale-like or granular substance is blended in an amount of about 1 to 200 parts by weight with respect to 100 parts by weight of a composition such as a sealing material composition or an adhesive composition.
- a composition such as a sealing material composition or an adhesive composition.
- the blending amount is appropriately selected depending on the size of each scale-like or granular substance, the material of the outer wall, the pattern, and the like.
- the scale-like or granular substance natural products such as silica sand and mica, synthetic rubber, synthetic resin, and inorganic materials such as alumina are used. In order to enhance the designability when filling the joint, it is colored in an appropriate color according to the material and pattern of the outer wall.
- a balloon preferably having an average particle size of 0.1 mm or more
- the surface becomes sandy or sandstone-like, and the weight can be reduced.
- Preferred diameters, blending amounts, materials, etc. of the balloon are as follows as described in JP-A-10-251618.
- the balloon is a spherical filler with a hollow interior.
- the balloon material include inorganic materials such as glass, shirasu, and silica, and organic materials such as phenol resin, urea resin, polystyrene, and saran, but are not limited thereto.
- an inorganic material and an organic material can be combined, or a plurality of layers can be formed by stacking.
- An inorganic or organic balloon or a combination of these can be used.
- the balloons used may be the same balloon or a mixture of different types of balloons.
- the balloon can be used by processing or coating the surface thereof, or can be used by treating the surface with various surface treatment agents.
- an organic balloon may be coated with calcium carbonate, talc, titanium oxide or the like, or an inorganic balloon may be surface-treated with an adhesion-imparting agent.
- the balloon preferably has a particle size of 0.1 mm or more.
- the thing of about 0.2 mm to 5.0 mm and about 0.5 mm to 5.0 mm can also be used. If it is less than 0.1 mm, even if it is blended in a large amount, it may only increase the viscosity of the composition and the rough feeling may not be exhibited.
- the blending amount of the balloon can be easily determined according to the desired degree of sanding tone or sandstone tone. In general, it is desirable to blend those having a particle size of 0.1 mm or more in a ratio of 5 to 25 vol% in terms of volume concentration in the composition.
- volume concentration of the balloon When the volume concentration of the balloon is less than 5 vol%, there is no feeling of roughness, and when it exceeds 25 vol%, the viscosity of the sealing material and the adhesive becomes high, the workability is poor, the modulus of the cured product is also high, and the sealing material and bonding The basic performance of the agent tends to be impaired.
- the volume concentration with particularly preferable balance with the basic performance of the sealing material is 8 to 22 vol%.
- the anti-slip agent as described in JP-A-2000-154368 and the surface of a cured product as described in JP-A-2001-164237 are matted to give an uneven state.
- An amine compound for obtaining a state particularly a primary and / or secondary amine having a melting point of 35 ° C. or higher can be added.
- balloons are disclosed in JP-A-2-129262, JP-A-4-8788, JP-A-4-173867, JP-A-5-1225, JP-A-7-113033, JP-A-9-53063, JP-A-10-10. -251618, JP-A No. 2000-154368, JP-A No. 2001-164237, WO 97/05201, and the like.
- the cured product can form irregularities on the surface and improve the design.
- Preferred diameters, blending amounts, materials and the like of the cured sealant particles are as follows as described in JP-A No. 2001-115142.
- the diameter is preferably about 0.1 mm to 1 mm, more preferably about 0.2 to 0.5 mm.
- the blending amount is preferably 5 to 100% by weight, more preferably 20 to 50% by weight in the curable composition.
- the material include urethane resin, silicone, modified silicone, polysulfide rubber and the like, and are not limited as long as they are used for the sealing material, but a modified silicone-based sealing material is preferable.
- a silicate can be used for the composition of this invention.
- This silicate acts as a cross-linking agent and has a function of improving the resilience, durability, and creep resistance of the organic polymers that are the components (A) and (B) of the present invention. Furthermore, it has the effect of improving adhesiveness, water-resistant adhesiveness, and adhesive durability under high temperature and high humidity conditions.
- As the silicate tetraalkoxysilane or a partial hydrolysis condensate thereof can be used.
- the amount used is 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the total of the components (A) and (B).
- silicate examples include, for example, tetramethoxysilane, tetraethoxysilane, ethoxytrimethoxysilane, dimethoxydiethoxysilane, methoxytriethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n- Examples thereof include tetraalkoxysilanes (tetraalkyl silicates) such as butoxysilane, tetra-i-butoxysilane, and tetra-t-butoxysilane, and partial hydrolysis condensates thereof.
- the partial hydrolysis-condensation product of tetraalkoxysilane is more preferable because the restoring effect, durability, and creep resistance of the present invention are greater than those of tetraalkoxysilane.
- Examples of the partially hydrolyzed condensate of tetraalkoxysilane include those obtained by adding water to tetraalkoxysilane and condensing it by partial hydrolysis according to an ordinary method.
- a commercially available product can be used as the partially hydrolyzed condensate of the organosilicate compound.
- Examples of such condensates include methyl silicate 51 and ethyl silicate 40 (both manufactured by Colcoat Co., Ltd.).
- a physical property modifier that adjusts the tensile properties of the cured product to be produced may be added as necessary.
- the physical property modifier is not particularly limited, but examples thereof include alkylalkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; dimethyldiisopropenoxysilane, methyltriisopropenoxy Silanes, alkylisopropenoxysilanes such as ⁇ -glycidoxypropylmethyldiisopropenoxysilane, ⁇ -glycidoxypropylmethyldimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyldimethylmethoxy Silane, ⁇ -aminopropyltrimethoxysilane, N- ( ⁇ -aminoethyl) amino
- a compound that generates a compound having a monovalent silanol group in the molecule by hydrolysis has an action of reducing the modulus of the cured product without deteriorating the stickiness of the surface of the cured product.
- Particularly preferred are compounds that produce trimethylsilanol.
- Examples of the compound that generates a compound having a monovalent silanol group in the molecule by hydrolysis include compounds described in JP-A-5-117521.
- derivatives of alkyl alcohols such as hexanol, octanol, decanol, and the like, which generate a silicon compound that generates R 3 SiOH such as trimethylsilanol by hydrolysis, and trimethylol described in JP-A-11-241029
- examples thereof include a compound of a polyhydric alcohol having 3 or more hydroxy groups such as propane, glycerin, pentaerythritol or sorbitol, which generates a silicon compound that generates R 3 SiOH such as trimethylsilanol by hydrolysis.
- the physical property modifier is used in the range of 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, with respect to 100 parts by weight of the total of component (A) and component (B).
- a thixotropic agent may be added to the curable composition of the present invention as necessary to prevent sagging and improve workability.
- the anti-sagging agent is not particularly limited, and examples thereof include polyamide waxes; hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate, and barium stearate.
- thixotropy is high. A composition having good workability can be obtained.
- thixotropic agents anti-sagging agents
- the thixotropic agent is used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight as the total of the components (A) and (B).
- a compound containing an epoxy group in one molecule can be used.
- the restorability of the cured product can be improved.
- the compound having an epoxy group include epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, compounds shown in epichlorohydrin derivatives, and mixtures thereof.
- epoxidized soybean oil epoxidized linseed oil, bis (2-ethylhexyl) -4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxy octyl stearate, Examples thereof include epoxy butyl stearate. Of these, E-PS is particularly preferred.
- the epoxy compound is preferably used in the range of 0.5 to 30 parts by weight based on 100 parts by weight of the total of the component (A) and the component (B).
- a photocurable material can be used in the composition of the present invention.
- a photocurable material is used, a film of the photocurable material is formed on the surface of the cured product, and the stickiness and weather resistance of the cured product can be improved.
- a photocurable substance is a substance that undergoes a chemical change in its molecular structure in a very short time due to the action of light, resulting in a change in physical properties such as curing. Many compounds such as organic monomers, oligomers, resins or compositions containing them are known as this type of compound, and any commercially available compound can be adopted. Representative examples include unsaturated acrylic compounds, polyvinyl cinnamates, azide resins, and the like.
- Unsaturated acrylic compounds include monomers, oligomers or mixtures thereof having one or several acrylic or methacrylic unsaturated groups, including propylene (or butylene, ethylene) glycol di (meth) acrylate, neopentyl Examples thereof include monomers such as glycol di (meth) acrylate or oligoesters having a molecular weight of 10,000 or less.
- Aronix M-210 special acrylate (bifunctional) Aronix M-210, Aronix M-215, Aronix M-220, Aronix M-233, Aronix M-240, Aronix M-245; (Trifunctional) Aronix M -305, Aronix M-309, Aronix M-310, Aronix M-315, Aronix M-320, Aronix M-325, and (Multifunctional) Aronix M-400, etc., but especially contain acrylic functional groups The compound which contains 3 or more same functional groups on average in 1 molecule is preferable.
- Examples of the polyvinyl cinnamates include photosensitive resins having a cinnamoyl group as a photosensitive group, and those obtained by esterifying polyvinyl alcohol with cinnamic acid, as well as many polyvinyl cinnamate derivatives.
- the azide resin is known as a photosensitive resin having an azide group as a photosensitive group.
- a photosensitive resin in addition to a rubber photosensitive solution in which a diazide compound is added as a photosensitive agent, a “photosensitive resin” (March 17, 1972).
- the photocurable substance is used in an amount of 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the total of the components (A) and (B). If it is less than 1 part by weight, there is no effect of improving the weather resistance, and if it is more than 10 parts by weight, the cured product tends to be too hard and tends to crack.
- an oxygen curable substance can be used.
- the oxygen curable substance include unsaturated compounds that can react with oxygen in the air.
- the oxygen curable substance reacts with oxygen in the air to form a cured film near the surface of the cured product. And prevents dust from adhering.
- oxygen curable substance examples include drying oils typified by drill oil and linseed oil, various alkyd resins obtained by modifying the compounds; acrylic polymers and epoxy resins modified with drying oils , Silicone resins; 1,2-polybutadiene, 1,4-polybutadiene, polymers of C5 to C8 diene obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, 1,3-pentadiene, etc.
- drying oils typified by drill oil and linseed oil, various alkyd resins obtained by modifying the compounds
- acrylic polymers and epoxy resins modified with drying oils Silicone resins
- 1,2-polybutadiene, 1,4-polybutadiene polymers of C5 to C8 diene obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, 1,3-pentadiene, etc.
- Liquid polymers liquid copolymers such as NBR and SBR obtained by copolymerizing monomers such as acrylonitrile and styrene copolymerizable with these diene compounds so that the main component is a diene compound
- various modified products thereof maleinized modified products, boiled oil modified products, etc.
- drill oil and liquid diene polymers are particularly preferable.
- the effect may be enhanced if a catalyst for promoting the oxidative curing reaction or a metal dryer is used in combination.
- Examples of these catalysts and metal dryers include metal salts such as cobalt naphthenate, lead naphthenate, zirconium naphthenate, cobalt octylate, zirconium octylate, and amine compounds.
- the amount of the oxygen curable substance used is preferably in the range of 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts per 100 parts by weight of the total of the components (A) and (B). Parts by weight. When the amount used is less than 0.1 parts by weight, the contamination is not sufficiently improved, and when it exceeds 10 parts by weight, the tensile properties of the cured product tend to be impaired.
- an oxygen curable substance is preferably used in combination with a photocurable substance.
- a flame retardant such as a phosphorus plasticizer such as ammonium polyphosphate and tricresyl phosphate, aluminum hydroxide, magnesium hydroxide, and thermally expandable graphite can be added to the curable composition of the present invention.
- the said flame retardant may be used independently and may be used together 2 or more types.
- the flame retardant is used in the range of 5 to 100 parts by weight, preferably 10 to 50 parts by weight with respect to 100 parts by weight of the total of the components (A) and (B).
- a solvent can be used for the purpose of reducing the viscosity of the composition, increasing thixotropy, and improving workability.
- the solvent is not particularly limited, and various compounds can be used. Specific examples include hydrocarbon solvents such as toluene, xylene, heptane, hexane, petroleum solvents, halogen solvents such as trichloroethylene, ester solvents such as ethyl acetate and butyl acetate, acetone, methyl ethyl ketone, and methyl isobutyl ketone.
- Examples include ketone solvents, alcohol solvents such as methanol, ethanol and isopropyl alcohol, and silicone solvents such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane. These solvents may be used alone or in combination of two or more.
- the blending amount of the solvent is preferably 3 parts by weight or less, more preferably 1 part by weight or less with respect to 100 parts by weight of the total of the component (A) and the component (B). Most preferably it is not included.
- various additives may be added as necessary for the purpose of adjusting various physical properties of the curable composition or the cured product.
- additives include, for example, curability regulators, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposers, lubricants, pigments, foaming agents, and anti-anticides. And fungicides.
- curability regulators include, for example, curability regulators, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposers, lubricants, pigments, foaming agents, and anti-anticides. And fungicides.
- These various additives may be used alone or in combination of two or more.
- Specific examples other than the specific examples of the additives listed in this specification include, for example, JP-B-4-69659, JP-B-7-108928, JP-A-63-254149, JP-A-62-2904, It is described in Japanese Laid-Open Patent Publication No. 2001
- the curable composition of the present invention can also be prepared as a one-component type in which all the blended components are pre-blended and sealed and cured by moisture in the air after construction. It is also possible to prepare a two-component type in which components such as a plasticizer and water are blended and the compounding material and the polymer composition are mixed before use. From the viewpoint of workability, a one-component type is preferable.
- the curable composition When the curable composition is of a one-component type, all the ingredients are pre-blended, so the water-containing ingredients are dehydrated and dried before use, or dehydrated during decompression or the like during compounding and kneading. Is preferred.
- the curable composition When the curable composition is a two-component type, it is not necessary to add a curing catalyst to the main component containing a polymer having a reactive silicon group, so gelation is possible even if some moisture is contained in the compounding agent. However, when long-term storage stability is required, dehydration and drying are preferable.
- heat drying method or vacuum dehydration method for solid materials such as powders, dehydration method using vacuum zeolite or activated zeolite, silica gel, quick lime, magnesium oxide for liquid materials
- the method is preferred.
- An alkoxysilane compound such as glycidoxypropyltrimethoxysilane may be added and reacted with water for dehydration.
- an oxazolidine compound such as 3-ethyl-2-methyl-2- (3-methylbutyl) -1,3-oxazolidine may be blended and reacted with water for dehydration.
- a small amount of an isocyanate compound may be blended to react with an isocyanate group and water for dehydration. Addition of an alkoxysilane compound, an oxazolidine compound, and an isocyanate compound improves storage stability.
- the amount of the dehydrating agent, particularly the silicon compound that can react with water such as vinyltrimethoxysilane, is 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight per 100 parts by weight of component (A). The range of is preferable.
- the method for preparing the curable composition of the present invention is not particularly limited.
- the above-described components are blended and kneaded using a mixer, roll, kneader or the like at room temperature or under heating, or a small amount of a suitable solvent is used. Ordinary methods such as dissolving and mixing the components may be employed.
- the curable composition of the present invention When the curable composition of the present invention is exposed to the atmosphere, it forms a three-dimensional network structure by the action of moisture, and is cured into a solid having rubbery elasticity.
- the curable composition of the present invention is a pressure-sensitive adhesive, a sealing material for buildings, ships, automobiles, roads, etc., an adhesive, a mold preparation, a vibration-proof material, a vibration-damping material, a sound-proof material, a foam material, a paint, and a spray material. Can be used for etc. Since the hardened
- electrical and electronic parts materials such as solar cell backside sealing materials, electrical insulation materials such as insulation coating materials for electric wires and cables, elastic adhesives, contact type adhesives, spray type sealing materials, crack repair materials, and tiles
- Adhesives powder paints, casting materials, medical rubber materials, medical adhesives, medical device sealing materials, food packaging materials, sealing materials for joints of exterior materials such as siding boards, coating materials, primers, electromagnetic wave shielding
- Conductive materials thermal conductive materials, hot melt materials, potting agents for electrical and electronic use, films, gaskets, various molding materials, and anti-rust / waterproof sealing materials for meshed glass and laminated glass end faces (cut parts)
- It can be used for various applications such as liquid sealants used in automobile parts, electrical parts, various machine parts and the like.
- the curable composition of the present invention is an adhesive for interior panels, an adhesive for exterior panels, an adhesive for tiles, an adhesive for stonework, an adhesive for ceiling finishing, an adhesive for floor finishing, and an adhesive for wall finishing.
- the cured product obtained from the curable composition of the present application is excellent in paint contamination, and the silica sand adhesion amount is 10 mg / cm 2 or less, and a more excellent cured product can obtain a cured product of less than 2 mg / cm 2 .
- the paint contamination evaluation method was as follows: The curable composition was allowed to stand at 23 ° C. and 50% RH for 3 days and then cured at 50 ° C. for 4 days. A water-based acrylic emulsion paint (trade name “please coat”, manufactured by SK Kaken Co., Ltd.) was applied to the surface of the sheet, and was further left for 7 days under conditions of 23 ° C. and 50% RH. Thereafter, 67 black made by Shinto Porcelain Co., Ltd. was used as silica sand, and the sample surface was uniformly applied. After 3 hours, the amount of silica sand adhering when the silica sand was lightly wiped with a brush was measured.
- the obtained unpurified polypropylene oxide having methallyl group only at one end was mixed and stirred with 300 parts by weight of n-hexane and 300 parts by weight of water, and then water was removed by centrifugation. Further, 300 parts by weight of water was mixed and stirred in the hexane solution, and after removing water again by centrifugation, hexane was removed by vacuum devolatilization. As a result, a polypropylene oxide having a methallyl group at one end and a number average molecular weight of about 7,500 in terms of polystyrene by GPC was obtained.
- polypropylene oxide having a methallyl group only at one terminal end For 100 parts by weight of polypropylene oxide having a methallyl group only at one terminal end, 2.3 parts by weight of methyldimethoxysilane and 90 parts at 90 ° C. for 5 hours using 150 ppm of an isopropanol solution having a platinum content of 3 wt% of a platinum vinylsiloxane complex as a catalyst. By reacting, a polyoxypropylene polymer (polymer A) having an average of about 1.0 methyldimethoxysilyl groups in the molecule was obtained.
- the obtained unpurified polypropylene oxide having an allyl group only at one end was mixed and stirred with 300 parts by weight of n-hexane and 300 parts by weight of water, and then water was removed by centrifugation. Further, 300 parts by weight of water was mixed and stirred in the hexane solution, and after removing water again by centrifugation, hexane was removed by vacuum devolatilization. As a result, a polypropylene oxide having an allyl group at one end and a polystyrene-reduced number average molecular weight of about 7,500 by GPC was obtained.
- Example 1 100 parts by weight of the polymer P-1 obtained in Synthesis Example 6, 55 parts by weight of the polymer A obtained in Synthesis Example 1, and surface-treated colloidal calcium carbonate (trade name: Hakujyo Hana CCR, manufactured by Shiroishi Kogyo Co., Ltd.) Part by weight, 20 parts by weight of titanium oxide (made by Ishihara Sangyo Co., Ltd., trade name: Typek R-820), 2 parts by weight of an anti-sagging agent (made by Enomoto Kasei Co., Ltd., trade name: Disparon 6500) 1 part by weight of an absorbent (manufactured by BASF Japan Ltd., trade name: TINUVIN 326) and 1 part by weight of a hindered amine light stabilizer (manufactured by Sankyo Lifetech Co., Ltd., trade name: Sanol LS770) are mixed and kneaded sufficiently.
- titanium oxide made by Ishihara Sangyo Co., Ltd., trade name: Typek R-820
- Aminopropyltrimethoxysilane (Momentive Performance Materials, trade name: Silquest A-1120) 3 parts by weight, dibutyltin bisacetylacetonate (manufactured by Nitto Kasei Kogyo Co., Ltd., trade name: Neostan as a curing catalyst) 2 parts by weight of U-220H) was added and kneaded to obtain a curable composition.
- the skinning time, residual tack (surface stickiness), dumbbell tensile properties, and paint stain resistance after 1 day, 3 days and 7 days were measured according to the following methods.
- Example 2 (Comparative Example 1) to (Comparative Example 4)
- a curable composition was obtained in the same manner as in Example 1 except that the polymer or plasticizer shown in Table 1 was used instead of the polymer A in Example 1, and the same evaluation was performed.
- Example 3 70 parts by weight of the polymer P-1 obtained in Synthesis Example 6, 30 parts by weight of the polymer B obtained in Synthesis Example 2, and a surface-treated colloidal calcium carbonate (manufactured by Shiroishi Kogyo Co., Ltd., trade name: Hakujyo Hana CCR) 120 Parts by weight, titanium oxide (made by Ishihara Sangyo Co., Ltd., trade name: Taipei R-820), 20 parts by weight, phthalate ester plasticizer (made by Jay Plus Co., Ltd., trade name: DIDP), 55 parts by weight, sauce 2 parts by weight of an inhibitor (manufactured by Enomoto Kasei Co., Ltd., trade name: Disparon 6500), 1 part by weight of a benzotriazole-based ultraviolet absorber (trade name: TINUVIN 326, manufactured by BASF Japan Ltd.), a hindered amine light stabilizer (Sankyo) Life Tech Co., Ltd., trade name: Sanol LS770
- Example 4 Example 4 to (Example 5), (Comparative Example 5) to (Comparative Example 8) A curable composition was obtained in the same manner as in Example 3 except that the polymers shown in Table 2 were used instead of the polymer P-1 and polymer B in Example 3, and the same evaluation was performed.
- Example 6 (Example 6), (Example 7), (Comparative Example 9)
- Example 3 The same method as in Example 3, except that 100 parts of the polymer P-1 in Example 3 was used, the amount or type of the polymer B was changed as shown in Table 2, and no phthalate ester plasticizer was used.
- the curable composition was obtained and the same evaluation was performed.
- the main agent was filled so that bubbles would not enter a 100 ml cup.
- BS viscometer manufactured by Tokimec
- rotor No. 7 was used to measure the viscosity at 1 rpm, 2 rpm, and 10 rpm of each composition under the conditions of 23 ° C. and 50% RH.
- the above curable composition was stretched with a spatula to a thickness of about 3 mm under conditions of 23 ° C. and 50% RH, and the surface of the curable composition was lightly touched over time using a microspatula. The time until the micro spatula was not reached was measured.
- the curable composition obtained above was stretched to a thickness of about 3 mm and left under conditions of 23 ° C. and 50% RH.
- the surface was lightly touched with a fingertip after 1 day, 3 days, and 7 days, and the degree of stickiness was evaluated.
- the stickiness was expressed by eight-level numbers, 8 being no stickiness at all, 5 being slightly sticky, 3 being sticky and 1 being not cured.
- the curable composition was made into a sheet-like test body having a thickness of 3 mm and completely cured by placing it in a 23 ° C., 50% RH condition for 3 days and further in a 50 ° C. dryer for 4 days. After punching into No. 3 dumbbell mold, a tensile test was performed at a tensile speed of 200 mm / min using an autograph manufactured by Shimadzu Corporation. 50% modulus, 100% modulus, strength at break, elongation at break (respectively, M50, M100, TB, and EB) were measured.
- a sheet-like test specimen having a thickness of 3 mm was prepared, left for 3 days at 23 ° C. and 50% RH, and then cured at 50 ° C. for 4 days.
- a water-based acrylic emulsion paint (trade name “please coat”, manufactured by SK Kaken Co., Ltd.) was applied to the surface of the sheet, and was further left for 7 days under conditions of 23 ° C. and 50% RH. Thereafter, 67 black made by Shinto Porcelain Co., Ltd. was used as silica sand, and the sample surface was uniformly applied. After 3 hours, the state when the silica sand was gently wiped with a brush was observed.
- Tables 1 and 2 show the compositions and physical properties of Examples and Comparative Examples.
- Table 1 shows the composition and physical properties of a curable composition using 55 parts by weight of various plasticizers with respect to 100 parts by weight of an organic polymer having reactive silicon groups at both ends.
- the polymer A claimed in the present invention which is an organic polymer having a silicon group only at one end and having a higher introduction rate, exhibits low modulus and high elongation properties, and also causes contamination of the coated film after curing. Good.
- polymer B having a reactive silicon group only at one end also exhibits substantially the same physical properties as polymer A.
- Comparative Example 1 using the phthalate ester plasticizer DIDP which has been used conventionally, the contamination of the paint was poor. Even in Comparative Example 2 using a PPG plasticizer having a molecular weight of 3,000, the paint contamination was improved over DIDP, but it was not sufficient.
- Polymer C is a polymer in which a reactive silicon group is introduced only at one end, but the paint contamination of Comparative Example 3 using this polymer was not perfect. Also in Comparative Example 4 using the polymer D, the paint stain resistance was not perfect. Moreover, the cured product has high modulus and high elongation, and is not suitable as a sealing material for buildings. This is presumably because the polymer D contains free molecules in which silicon groups are introduced at both ends and silicon groups are not introduced.
- Example 3 Example 4 and Comparative Example 5 in Table 2 show the physical properties when 30 parts by weight of a polymer containing reactive silicon groups is replaced with a reactive plasticizer. .
- Example 3 it can be considered that 30 parts by weight of 100 parts by weight of the polymer P-1 in Comparative Example 6 were replaced with the polymer B. Since the viscosity of Example 3 is low, the workability is good, and the cured product has a low modulus and a high elongation. Although Comparative Example 5 using the polymer C had the same effect, the restoration property showed a low value.
- the polymer E is obtained by introducing a reactive silyl via a methallyl group, and the silyl group content is the same as that of the polymer C.
- the resilience of Example 4 using this polymer E is significantly higher than the comparative example using the polymer C in the silyl group content. That is, the restoring property indicates that a specific structure near the silyl group contributes not the amount of silyl group introduced.
- Example 5 Comparative Example 7, and Comparative Example 8 are the results of performing the same evaluation by substituting the polymer P-2 for the polymer P-1. Even in this case, the difference in physical properties between the polymer B and the polymer C is the same, and it can be seen that the use of the component (A) having a specific reactive silicon group expresses the characteristics of high resilience. .
- Examples 6, 7 and 9 use 100 parts of polymer P-1, 55 parts by weight of a component having a reactive silyl group only at one end of the molecule, and a general phthalate ester. This is a system that does not use a plasticizer. Also in this case, it is shown that a curable composition exhibiting high resilience can be obtained by using the component (A) having a specific reactive silicon group.
- the curable composition of the present invention is a pressure-sensitive adhesive, a sealing material for buildings, ships, automobiles, roads, etc., an adhesive, a mold preparation, a vibration-proof material, a vibration-damping material, a sound-proof material, a foam material, a paint, and a spray material. Can be used for etc. Since the hardened
- electrical and electronic parts materials such as solar cell backside sealing materials, electrical insulation materials such as insulation coating materials for electric wires and cables, elastic adhesives, contact type adhesives, spray type sealing materials, crack repair materials, and tiles
- Adhesives powder paints, casting materials, medical rubber materials, medical adhesives, medical device sealing materials, food packaging materials, sealing materials for joints of exterior materials such as siding boards, coating materials, primers, electromagnetic wave shielding
- Conductive materials thermal conductive materials, hot melt materials, potting agents for electrical and electronic use, films, gaskets, various molding materials, and anti-rust / waterproof sealing materials for meshed glass and laminated glass end faces (cut parts)
- It can be used for various applications such as liquid sealants used in automobile parts, electrical parts, various machine parts and the like.
- the curable composition of the present invention is an adhesive for interior panels, an adhesive for exterior panels, an adhesive for tiles, an adhesive for stonework, an adhesive for ceiling finishing, an adhesive for floor finishing, and an adhesive for wall finishing.
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Abstract
Description
(I).数平均分子量が800~15,000で、一般式(1):
-Y-R1-CH(CH3)-CH2-Si(R2 3-a)Xa (1)
(式中、R1は水素、炭素、及び窒素からなる群より選択される1種以上を構成原子として含有する炭素数1から20の2価の有機基を示し、R2は炭素数1から20のアルキル基、炭素数6から20のアリール基、炭素数7から20のアラルキル基または-OSi(R’)3で示されるトリオルガノシロキシ基を示す。ここでR’は炭素数1から20の一価の炭化水素基であり3個のR’は同一であってもよく、異なっていてもよい。Xは水酸基または加水分解性基を示し、Xが二個以上存在するとき、それらは同一であってもよく、異なっていてもよい。Yはヘテロ原子であり、酸素原子または窒素原子から選択される。aは1~3の整数である)で示される反応性ケイ素基を一分子中に平均して0.5~1.2個未満含有する有機重合体(A)、
(II).有機重合体(A)の主鎖が、直鎖状であることを特徴とする、(I)に記載の有機重合体、
(III).有機重合体(A)の反応性ケイ素基が、実質的に有機重合体の片方の末端にのみ存在することを特徴とする、(I)または(II)に記載の有機重合体、
(IV).一般式(1)中に記載のR1がCH2であることを特徴とする、(I)~(III)のいずれかに記載の有機重合体、
(V).一般式(1)中に記載のYが酸素原子であることを特徴とする、(I)~(IV)のいずれかに記載の有機重合体、
(VI).一般式(1)中に記載のaが2であることを特徴とする、(I)~(V)のいずれかに記載の有機重合体、
(VII).有機重合体(A)の主鎖がポリオキシアルキレン系重合体、ポリアクリル系重合体、炭化水素系重合体のいずれか又は複数であることを特徴とする、(I)~(VI)のいずれかに記載の有機重合体、
(VIII).有機重合体(A)の主鎖がポリオキシプロピレン系重合体であることを特徴とする、(I)~(VII)のいずれかに記載の有機重合体、
(IX).有機重合体(A)が、1分子中に水酸基を1個のみ有する開始剤を用いて、複合金属シアン化物錯体触媒存在下でプロピレンオキシドを反応させたポリオキシプロピレン系重合体に、一般式(1)で示される反応性ケイ素基を導入して得られることを特徴とする、(I)~(VIII)のいずれかに記載の有機重合体、
(X).有機重合体(A)が、1分子中に水酸基を2個以上有する開始剤と、1分子中に水酸基を1個のみ有する開始剤を併用し、複合金属シアン化物錯体触媒存在下でプロピレンオキシドを反応させたポリオキシプロピレン系重合体に、一般式(1)で示される反応性ケイ素基を導入して得られることを特徴とする、(I)~(IX)のいずれかに記載の有機重合体、
(XI).有機重合体(A)の反応性ケイ素基が、メチルジメトキシシリル基であることを特徴とする、(I)~(X)のいずれかに記載の有機重合体、
(XII).(I)~(XI)のいずれかに記載の有機重合体(A)と、数平均分子量が5,000~50,000で、反応性ケイ素基を1分子中に平均して1.2個~5個含有する有機重合体(B)、を含む硬化性組成物、
(XIII).有機重合体(B)の主鎖がポリオキシアルキレン系重合体、ポリアクリル系重合体、炭化水素系重合体のいずれか又は複数であることを特徴とする、(XII)に記載の硬化性組成物、
(XIV).有機重合体(B)の反応性ケイ素基が、メチルジメトキシシリル基であることを特徴とする、(XII)~(XIII)のいずれかに記載の硬化性組成物、
(XV).有機重合体(A)100重量部に対して、有機重合体(B)を20~2000重量部使用することを特徴とする(XII)~(XIV)のいずれかに記載の硬化性組成物、
(XVI).フタル酸エステル系可塑剤を、有機重合体(A)100重量部に対して1~20重量部使用することを特徴とする、(XII)~(XV)のいずれかに記載の硬化性組成物、
(XVII).(XII)~(XVI)のいずれかに記載の硬化性組成物を用いた建築用シーリング材、
(XVIII).(XII)~(XVI)のいずれかに記載の硬化性組成物を用いたサイディングボードに施工されるシーリング材、
(XIX).(XII)~(XVI)のいずれかに記載の硬化性組成物を用いた石目地用シーリング材、
(XX).(XII)~(XVI)のいずれかに記載の硬化性組成物を硬化させた硬化物であって、下記方法で評価した珪砂付着量の値が10mg/cm2以下であることを特徴とする硬化物:
(評価方法)硬化性組成物を23℃、50%RH条件下で3日間放置した後、50℃で4日間硬化させる。当該シートの表面に、水性アクリルエマルション塗料(エスケー化研(株)製、商品名「プリーズコート」)を塗布し、さらに23℃、50%RH条件下で7日間放置する。7日間放置の後、珪砂として新東陶料(株)製67ブラックを当該シートの表面に均一に塗布する。3時間経過後に、刷毛で珪砂を軽く拭き取った時の単位面積当たりの付着量(mg/cm2)を測定する、
に関する。
-Y-R1-CH(CH3)-CH2-Si(R2 3-a)Xa (1)
(式中、R1は水素、炭素、及び窒素からなる群より選択される1種以上を構成原子として含有する炭素数1から20の2価の有機基を示し、R2は炭素数1から20のアルキル基、炭素数6から20のアリール基、炭素数7から20のアラルキル基または-OSi(R’)3で示されるトリオルガノシロキシ基を示す。ここでR’は炭素数1から20の一価の炭化水素基であり3個のR’は同一であってもよく、異なっていてもよい。Xは水酸基または加水分解性基を示し、Xが二個以上存在するとき、それらは同一であってもよく、異なっていてもよい。Yはヘテロ原子であり、酸素原子または窒素原子から選択される。aは1~3の整数である)で示される基である。
-SiR2 3-aXa (2)
(R2は、それぞれ独立に炭素原子数1から20のアルキル基、炭素原子数6から20のアリール基、炭素原子数7から20のアラルキル基、または、-OSi(R’)3(R’は、それぞれ独立に炭素原子数1から20の炭化水素基である)で示されるトリオルガノシロキシ基である。また、Xは、それぞれ独立にヒドロキシ基または加水分解性基である。更に、aは1~3の整数である)で表される基があげられる。
H-(SiR3 2O)mSiR3 2-R4-SiX3 (3)
(Xは前記に同じ。2m+2個のR3は、それぞれ独立に炭化水素基であり、入手性およびコストの点から、炭素原子数1から20の炭化水素基が好ましく、炭素原子数1から8の炭化水素基がより好ましく、炭素原子数1から4の炭化水素基が特に好ましい。R4は2価の有機基であり、入手性およびコストの点から、炭素原子数1から12の2価の炭化水素基が好ましく、炭素原子数2から8の2価の炭化水素基がより好ましく、炭素原子数2の2価の炭化水素基が特に好ましい。また、mは0から19の整数であり、入手性およびコストの点から、1が好ましい)で表されるシラン化合物は、不均化反応が進まない。この為、(I)の合成法で、3個の加水分解性基が1つのケイ素原子に結合している基を導入する場合には、一般式(3)で表されるシラン化合物を用いることが好ましい。一般式(3)で示されるシラン化合物の具体例としては、1-[2-(トリメトキシシリル)エチル]-1,1,3,3-テトラメチルジシロキサン、1-[2-(トリメトキシシリル)プロピル]-1,1,3,3-テトラメチルジシロキサン、1-[2-(トリメトキシシリル)ヘキシル]-1,1,3,3-テトラメチルジシロキサンが挙げられる。
-R5-O- (4)
(R5は、炭素原子数1から14の直鎖状もしくは分岐アルキレン基である)で示される繰り返し単位を有する重合体であり、一般式(4)におけるR5は、炭素原子数1から14の、更には2から4の、直鎖状もしくは分岐アルキレン基が好ましい。一般式(4)で示される繰り返し単位の具体例としては、
-CH2O-、-CH2CH2O-、-CH2CH(CH3)O-、-CH2CH(C2H5)O-、-CH2C(CH3)2O-、-CH2CH2CH2CH2O-
等が挙げられる。ポリオキシアルキレン系重合体の主鎖骨格は、1種類だけの繰り返し単位からなってもよいし、2種類以上の繰り返し単位からなってもよい。特にシーリング材等に使用される場合には、プロピレンオキシド重合体を主成分とする重合体から成るものが非晶質であることや比較的低粘度である点から好ましい。
-CH2-C(R6)(COOR7)- (5)
(R6は水素原子またはメチル基、R7は炭素原子数1から8のアルキル基を示す)で表される炭素原子数1から8のアルキル基を有する(メタ)アクリル酸エステル単量体単位と、下記一般式(6):
-CH2-C(R6)(COOR8)- (6)
(R6は前記に同じ、R8は炭素原子数9以上のアルキル基を示す)で表される炭素原子数9以上のアルキル基を有する(メタ)アクリル酸エステル単量体単位からなる共重合体に、反応性ケイ素基を有するポリオキシアルキレン系重合体をブレンドして製造する方法である。
-NR9-C(=O)- (7)
(R9は有機基または水素原子を表す)で表される基である。
W-R10-SiR2 3-aXa (8)
(R2、X、aは前記と同じ。R10は2価の有機基であり、より好ましくは炭素原子数1から20の炭化水素基である。Wはヒドロキシ基、カルボキシ基、メルカプト基およびアミノ基(1級または2級)から選ばれた活性水素含有基である)で表されるケイ素化合物のW基を反応させる方法により製造されるものを挙げることができる。この製造方法に関連した、有機重合体の公知の製造法を例示すると、特公昭46-12154号(米国特許3632557号)、特開昭58-109529号(米国特許4374237号)、特開昭62-13430号(米国特許4645816号)、特開平8-53528号(EP0676403)、特開平10-204144号(EP0831108)、特表2003-508561(米国特許6197912号)、特開平6-211879号(米国特許5364955号)、特開平10-53637号(米国特許5756751号)、特開平11-100427号、特開2000-169544号、特開2000-169545号、特開2002-212415号、特許第3313360号、米国特許4067844号、米国特許3711445号、特開2001-323040号等が挙げられる。
O=C=N-R10-SiR2 3-aXa (9)
(R10、R2、X、aは前記に同じ)で示される反応性ケイ素基含有イソシアネート化合物とを反応させることにより製造されるものを挙げることができる。この製造方法に関連した、有機重合体の公知の製造法を例示すると、特開平11-279249号(米国特許5990257号)、特開2000-119365号(米国特許6046270号)、特開昭58-29818号(米国特許4345053号)、特開平3-47825号(米国特許5068304号)、特開平11-60724号、特開2002-155145号、特開2002-249538号、WO03/018658、WO03/059981等が挙げられる。
-NR11-C(=O)- (10)
(R11は水素原子または置換あるいは非置換の有機基を表す)で表される基を有する。この構造は極性が比較的高いため、硬化物の強度や基材への接着性が高くなる傾向にあり望ましい。
本発明の硬化性組成物には、必要に応じて垂れを防止し、作業性を良くするためにチクソ性付与剤(垂れ防止剤)を添加しても良い。垂れ防止剤としては特に限定されないが、例えば、ポリアミドワックス類;水添ヒマシ油誘導体類;ステアリン酸カルシウム、ステアリン酸アルミニウム、ステアリン酸バリウム等の金属石鹸類等が挙げられる。また、特開平11-349916号公報に記載されているような粒子径10から500μmのゴム粉末や、特開2003-155389号公報に記載されているような有機質繊維を用いると、チクソ性が高く作業性の良好な組成物が得られる。これらチクソ性付与剤(垂れ防止剤)は単独で用いてもよく、2種以上併用してもよい。チクソ性付与剤は(A)成分と(B)成分の合計100重量部に対して、0.1から10重量部の範囲で使用される。
ポリケイ皮酸ビニル類としては、シンナモイル基を感光基とする感光性樹脂でありポリビニルアルコールをケイ皮酸でエステル化したものの他、多くのポリケイ皮酸ビニル誘導体が例示される。アジド化樹脂は、アジド基を感光基とする感光性樹脂として知られており、通常はジアジド化合物を感光剤として加えたゴム感光液の他、「感光性樹脂」(昭和47年3月17日出版、印刷学会出版部発行、第93頁から、第106頁から、第117頁から)に詳細な例示があり、これらを単独または混合し、必要に応じて増感剤を加えて使用することができる。なお、ケトン類、ニトロ化合物などの増感剤やアミン類などの促進剤を添加すると、効果が高められる場合がある。光硬化性物質は、(A)成分と(B)成分の合計100重量部に対して0.1から10重量部、好ましくは0.5から5重量部の範囲で使用するのがよく、0.1重量部以下では耐候性を高める効果はなく、10重量部以上では硬化物が硬くなりすぎて、ヒビ割れを生じる傾向がある。
分子量約1,200のポリオキシプロピレングリコールモノブチルエーテル(三洋化成工業(株)製、商品名:ニューポールLB-285)を開始剤とし、亜鉛ヘキサシアノコバルテートグライム錯体触媒にてプロピレンオキシドの重合を行い、数平均分子量約7,500(送液システムとして東ソー製HLC-8120GPCを用い、カラムは東ソー製TSK-GEL Hタイプを用い、溶媒はTHFを用いて測定したポリスチレン換算分子量)のポリプロピレンオキシドを得た。続いて、この水酸基を有するポリプロピレンオキシドの水酸基に対して1.2倍当量のNaOMeのメタノール溶液を添加してメタノールを留去し、更に3-クロロ-2-メチル-1-プロペンを添加して末端の水酸基をメタリル基に変換した。
数平均分子量14,600(上記と同じ方法にて測定)のポリオキシプロピレングリコールとn-ブタノールをそれぞれ重量比で10:1の割合で混合したものを開始剤とし、亜鉛ヘキサシアノコバルテートグライム錯体触媒にてプロピレンオキシドの重合を行い、数平均分子量約8,000(上記と同じ方法にて測定)のポリプロピレンオキシドを得た。続いて、この水酸基を有するポリプロピレンオキシドの水酸基に対して1.2倍当量のNaOMeのメタノール溶液を添加してメタノールを留去し、更に3-クロロ-2-メチル-1-プロペンを添加して末端の水酸基をメタリル基に変換した。
分子量約1,200のポリオキシプロピレングリコールモノブチルエーテル(三洋化成工業(株)製、商品名:ニューポールLB-285)を開始剤とし、亜鉛ヘキサシアノコバルテートグライム錯体触媒にてプロピレンオキシドの重合を行い、数平均分子量約7,500(上記と同じ方法にて測定)のポリプロピレンオキシドを得た。続いて、この水酸基を有するポリプロピレンオキシドの水酸基に対して1.2倍当量のNaOMeのメタノール溶液を添加してメタノールを留去し、更に塩化アリルを添加して末端の水酸基をアリル基に変換した。
ポリプロピレングリコールを開始剤とし、亜鉛ヘキサシアノコバルテートグライム錯体触媒にてプロピレンオキシドの重合を行い、数平均分子量約7,500(上記と同じ方法にて測定)のポリプロピレンオキシドを得た。続いて、この水酸基末端ポリプロピレンオキシドの水酸基に対して1.2倍当量のNaOMeのメタノール溶液を添加してメタノールを留去し、更に塩化アリルを添加して末端の水酸基をアリル基に変換した。
数平均分子量14,600(上記と同じ方法にて測定)のポリオキシプロピレングリコールとn-ブタノールをそれぞれ重量比で10:1の割合で混合したものを開始剤とし、亜鉛ヘキサシアノコバルテートグライム錯体触媒にてプロピレンオキシドの重合を行い、数平均分子量約8,000(上記と同じ方法にて測定)のポリプロピレンオキシドを得た。続いて、この水酸基を有するポリプロピレンオキシドの水酸基に対して1.2倍当量のNaOMeのメタノール溶液を添加してメタノールを留去し、更に3-クロロ-2-メチル-1-プロペンを添加して末端の水酸基をメタリル基に変換した。
ポリプロピレングリコールを開始剤とし、亜鉛ヘキサシアノコバルテートグライム錯体触媒にてプロピレンオキシドの重合を行い、数平均分子量約28,500(上記と同じ方法にて測定)のポリプロピレンオキシドを得た。続いて、この水酸基末端ポリプロピレンオキシドの水酸基に対して1.2倍当量のNaOMeのメタノール溶液を添加してメタノールを留去し、更に塩化アリルを添加して末端の水酸基をアリル基に変換した。
ポリプロピレングリコールを開始剤とし、亜鉛ヘキサシアノコバルテートグライム錯体触媒にてプロピレンオキシドの重合を行い、数平均分子量約28,500(上記と同じ方法にて測定)のポリプロピレンオキシドを得た。続いて、この水酸基末端ポリプロピレンオキシドの水酸基に対して1.2倍当量のNaOMeのメタノール溶液を添加してメタノールを留去し、更に3-クロロ-2-メチル-1-プロペンを添加して末端の水酸基をメタリル基に変換した。
合成例6で得られたポリマーP-1を100重量部、合成例1で得られたポリマーAを55重量部、表面処理膠質炭酸カルシウム(白石工業(株)製、商品名:白艶華CCR)120重量部、酸化チタン(石原産業(株)製、商品名:タイペークR-820)20重量部、タレ防止剤(楠本化成(株)製、商品名:ディスパロン6500)2重量部、ベンゾトリアゾール系紫外線吸収剤(BASFジャパン(株)製、商品名:TINUVIN326)1重量部、ヒンダードアミン系光安定剤(三共ライフテック(株)製、商品名:サノールLS770)1重量部、を混合して充分混練りした後、3本ペイントロールに3回通して分散させ、23℃50%RH条件下に一晩置いたものを主剤とした。この主剤の粘度を測定した後、脱水剤としてビニルトリメトキシシラン(モメンティブ・パフォーマンス・マテリアルズ社製、商品名:Silquest A-171)2重量部、接着性付与剤としてγ-(2-アミノエチル)アミノプロピルトリメトキシシラン(モメンティブ・パフォーマンス・マテリアルズ社製、商品名:Silquest A-1120)3重量部、硬化触媒としてジブチル錫ビスアセチルアセトナート(日東化成工業(株)製、商品名:ネオスタンU-220H)2重量部を加えて混練し、硬化性組成物を得た。この硬化性組成物の皮張り時間、1日後と3日後と7日後の残留タック(表面のべたつき)、ダンベル引張物性、塗料汚染性を下記の方法に従って測定した。
実施例1におけるポリマーAの代わりに、表1に示すポリマーもしくは可塑剤を用いること以外は、実施例1と同様の方法で硬化性組成物を得て、同様の評価を行った。
合成例6で得られたポリマーP-1を70重量部、合成例2で得られたポリマーBを30重量部、表面処理膠質炭酸カルシウム(白石工業(株)製、商品名:白艶華CCR)120重量部、酸化チタン(石原産業(株)製、商品名:タイペークR-820)20重量部、フタル酸エステル系可塑剤(ジェイ・プラス(株)製、商品名:DIDP)55重量部、タレ防止剤(楠本化成(株)製、商品名:ディスパロン6500)2重量部、ベンゾトリアゾール系紫外線吸収剤(BASFジャパン(株)製、商品名:TINUVIN326)1重量部、ヒンダードアミン系光安定剤(三共ライフテック(株)製、商品名:サノールLS770)1重量部、を混合して充分混練りした後、3本ペイントロールに3回通して分散させ、23℃50%RH条件下に一晩置いたものを主剤とした。この主剤の粘度を測定した後、脱水剤としてビニルトリメトキシシラン(モメンティブ・パフォーマンス・マテリアルズ社製、商品名:Silquest A-171)2重量部、接着性付与剤としてγ-(2-アミノエチル)アミノプロピルトリメトキシシラン(モメンティブ・パフォーマンス・マテリアルズ社製、商品名:Silquest A-1120)3重量部、硬化触媒としてジブチル錫ジラウレート(日東化成工業(株)製、商品名:ネオスタンU-100)1重量部を加えて混練し、硬化性組成物を得た。この硬化性組成物の1日後と3日後と7日後の残留タック(表面のべたつき)、ダンベル引張物性、復元性を下記の方法に従って測定した。
実施例3におけるポリマーP-1とポリマーBの代わりに、表2に示すポリマーを用いること以外は、実施例3と同様の方法で硬化性組成物を得て、同様の評価を行った。
実施例3におけるポリマーP-1を100部使用し、ポリマーBの量または種類を表2に示す通りに変更し、フタル酸エステル系可塑剤を使用しないこと以外は、実施例3と同様の方法で硬化性組成物を得て、同様の評価を行った。
100ml容のカップに泡が入らないように主剤を充填した。BS型粘度計(トキメック社製)とローターNo.7を用いて、23℃50%RH条件下で各組成物の1rpm、2rpm、10rpmでの粘度を測定した。
23℃、50%RH条件下にて上記硬化性組成物を厚みが約3mmになるようヘラを用いて伸ばし、ミクロスパテュラを用いて経時で硬化性組成物の表面に軽く触れ、組成物がミクロスパテュラについてこなくなるまでの時間を測定した。
上記で得られた硬化性組成物を厚み約3mmに伸ばし、23℃、50%RH条件下で放置した。1日後、3日後、7日後にその表面を指先で軽く触れ、べたつき程度を評価した。べたつき感は8段階の数字で表現し、8は全くべたつきが感じられない、5は少しべたつき感があり、3はべたつき感がきつい、1は硬化していない、を目安に判定した。
上記硬化性組成物を厚さ3mmのシート状試験体にして23℃、50%RH条件に3日間、さらに50℃乾燥機に4日間入れることで完全に硬化させた。3号ダンベル型に打ち抜いた後、島津(株)製オートグラフを用いて引張速度200mm/分で引張試験を行い、50%モジュラス、100%モジュラス、破断時の強度、破断時の伸び(それぞれ、M50、M100、TB、EBと示す)を測定した。
それぞれの硬化性組成物を用いて、厚さ3mmのシート状試験体を作成し、23℃、50%RH条件下で3日間放置した後、50℃で4日間硬化させた。このシートの表面に、水性アクリルエマルション塗料(エスケー化研(株)製、商品名「プリーズコート」)を塗布して、さらに、23℃、50%RH条件下で7日間放置した。その後、珪砂として新東陶料(株)製67ブラックを使用してサンプル表面に均一に塗布した。3時間経過後に、刷毛で珪砂を軽く拭き取った時の状態を観察した。塗料汚染性は5段階の数字で表現し、5:珪砂付着が全くなし(2mg/cm2未満)、3:珪砂が少し付着している(10mg/cm2以上かつ20mg/cm2未満)、1:一面に珪砂が多数付着(30mg/cm2以上)、を目安に判定した。
上記の引張物性と同様の作成方法で得た3号ダンベル型試験体について、60%伸張して23℃50%RH条件で24時間保持した。その後、伸張を開放し、同条件で放置して1時間後と24時間後に復元した程度を測定した。完全に元の状態に戻った場合は復元性100%、全く復元しなかった場合は0%となる。
Claims (20)
- 数平均分子量が800~15,000で、一般式(1):
-Y-R1-CH(CH3)-CH2-Si(R2 3-a)Xa (1)
(式中、R1は水素、炭素、及び窒素からなる群より選択される1種以上を構成原子として含有する炭素数1から20の2価の有機基を示し、R2は炭素数1から20のアルキル基、炭素数6から20のアリール基、炭素数7から20のアラルキル基または-OSi(R’)3で示されるトリオルガノシロキシ基を示す。ここでR’は炭素数1から20の一価の炭化水素基であり3個のR’は同一であってもよく、異なっていてもよい。Xは水酸基または加水分解性基を示し、Xが二個以上存在するとき、それらは同一であってもよく、異なっていてもよい。Yはヘテロ原子であり、酸素原子または窒素原子から選択される。aは1~3の整数である。)で示される反応性ケイ素基を一分子中に平均して0.5~1.2個未満含有する有機重合体(A)。 - 有機重合体(A)の主鎖が、直鎖状であることを特徴とする、請求項1に記載の有機重合体。
- 有機重合体(A)の反応性ケイ素基が、実質的に有機重合体の片方の末端にのみ存在することを特徴とする、請求項1または請求項2に記載の有機重合体。
- 一般式(1)中に記載のR1がCH2であることを特徴とする、請求項1~3のいずれかに記載の有機重合体。
- 一般式(1)中に記載のYが酸素原子であることを特徴とする、請求項1~4のいずれかに記載の有機重合体。
- 一般式(1)中に記載のaが2であることを特徴とする、請求項1~5のいずれかに記載の有機重合体。
- 有機重合体(A)の主鎖がポリオキシアルキレン系重合体、ポリアクリル系重合体、炭化水素系重合体のいずれか又は複数であることを特徴とする、請求項1~6のいずれかに記載の有機重合体。
- 有機重合体(A)の主鎖がポリオキシプロピレン系重合体であることを特徴とする、請求項1~7のいずれかに記載の有機重合体。
- 有機重合体(A)が、1分子中に水酸基を1個のみ有する開始剤を用いて、複合金属シアン化物錯体触媒存在下でプロピレンオキシドを反応させたポリオキシプロピレン系重合体に、一般式(1)で示される反応性ケイ素基を導入して得られることを特徴とする、請求項1~8のいずれかに記載の有機重合体。
- 有機重合体(A)が、1分子中に水酸基を2個以上有する開始剤と、1分子中に水酸基を1個のみ有する開始剤を併用し、複合金属シアン化物錯体触媒存在下でプロピレンオキシドを反応させたポリオキシプロピレン系重合体に、一般式(1)で示される反応性ケイ素基を導入して得られることを特徴とする、請求項1~9のいずれかに記載の有機重合体。
- 有機重合体(A)の反応性ケイ素基が、メチルジメトキシシリル基であることを特徴とする、請求項1~10のいずれかに記載の有機重合体。
- 請求項1~11のいずれかに記載の有機重合体(A)と、数平均分子量が5,000~50,000で、反応性ケイ素基を1分子中に平均して1.2個~5個含有する有機重合体(B)、を含む硬化性組成物。
- 有機重合体(B)の主鎖がポリオキシアルキレン系重合体、ポリアクリル系重合体、炭化水素系重合体のいずれか又は複数であることを特徴とする、請求項12に記載の硬化性組成物。
- 有機重合体(B)の反応性ケイ素基が、メチルジメトキシシリル基であることを特徴とする、請求項12~13のいずれかに記載の硬化性組成物。
- 有機重合体(A)100重量部に対して、有機重合体(B)を20~2000重量部使用することを特徴とする請求項12~14のいずれかに記載の硬化性組成物。
- フタル酸エステル系可塑剤を、有機重合体(A)100重量部に対して1~20重量部使用することを特徴とする、請求項12~15のいずれかに記載の硬化性組成物。
- 請求項12~16のいずれかに記載の硬化性組成物を用いた建築用シーリング材。
- 請求項12~16のいずれかに記載の硬化性組成物を用いたサイディングボードに施工されるシーリング材。
- 請求項12~16のいずれかに記載の硬化性組成物を用いた石目地用シーリング材。
- 請求項12~16のいずれかに記載の硬化性組成物を硬化させた硬化物であって、下記方法で評価した珪砂付着量の値が10mg/cm2以下であることを特徴とする硬化物:
(評価方法)硬化性組成物を23℃、50%RH条件下で3日間放置した後、50℃で4日間硬化させる。当該シートの表面に、水性アクリルエマルション塗料(エスケー化研(株)製、商品名「プリーズコート」)を塗布し、さらに23℃、50%RH条件下で7日間放置する。7日間放置の後、珪砂として新東陶料(株)製67ブラックを当該シートの表面に均一に塗布する。3時間経過後に、刷毛で珪砂を軽く拭き取った時の単位面積当たりの付着量(mg/cm2)を測定する。
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JP2015218310A (ja) * | 2014-05-20 | 2015-12-07 | 株式会社カネカ | 硬化性組成物およびその硬化物 |
JP2016098302A (ja) * | 2014-11-20 | 2016-05-30 | 株式会社カネカ | 硬化性組成物 |
JP2017503869A (ja) * | 2013-12-03 | 2017-02-02 | エボニック デグサ ゲーエムベーハーEvonik Degussa GmbH | 本質的に低下した粘度を有するアルコキシシリル含有接着剤/シーラント |
JPWO2016031913A1 (ja) * | 2014-08-29 | 2017-06-08 | 旭硝子株式会社 | 硬化性組成物の製造方法および硬化性組成物 |
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CN103261270B (zh) | 2016-01-20 |
JPWO2012081483A1 (ja) | 2014-05-22 |
US9365755B2 (en) | 2016-06-14 |
EP2653490A1 (en) | 2013-10-23 |
EP2653490B1 (en) | 2018-04-18 |
EP2653490A4 (en) | 2016-10-26 |
CN103261270A (zh) | 2013-08-21 |
US20130281591A1 (en) | 2013-10-24 |
JP5785954B2 (ja) | 2015-09-30 |
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