CN103687882B - Light-curing resin composition, and plumbing member and functional panel using same - Google Patents

Light-curing resin composition, and plumbing member and functional panel using same Download PDF

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Publication number
CN103687882B
CN103687882B CN201280035678.2A CN201280035678A CN103687882B CN 103687882 B CN103687882 B CN 103687882B CN 201280035678 A CN201280035678 A CN 201280035678A CN 103687882 B CN103687882 B CN 103687882B
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methyl
acrylate
resin composition
photocurable resin
aforementioned
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CN103687882A (en
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石原健延
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Bridgestone Corp
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Bridgestone Corp
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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
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/062—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
    • C08F299/065—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes from polyurethanes with side or terminal unsaturations
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/61—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes

Abstract

Provided are: a light-curing resin composition that exhibits improved water-repellency and slipperiness over the long term; and a plumbing member and functional panel using said light-curing resin composition. This light-curing resin composition contains the following: a (A) dimethyl silicone (meth)acrylate oligomer obtained by reacting (a) a silicone polyol, (b) isocyanate, and (c) a (meth)acrylate monomer that has a terminal functional group that can react with isocyanate; a (B) photopolymerizable oligomer and/or (C) photopolymerizable monomer that can copolymerize with the aforementioned (A) dimethyl silicone (meth)acrylate oligomer; and a (D) photopolymerization initiator.

Description

Photocurable resin composition and use its wet district component and functional panel
Technical field
The present invention relates to Photocurable resin composition and use its wet district component and functional panel, particularly relate to and can improve the Photocurable resin composition of water-repellancy and slipperiness (easily can remove the water skiing of surperficial water droplet) and use its wet district component and functional panel in long-time.
Background technology
The component that functional panel (panel) as material of construction is metope as the metope of buildings, ground or top ceiling and configures, the place according to its configuration has been endowed the various function such as soundproof effect, moisture control performance.Such functional panel, especially when being used as the bathroom of premises, toilet or Deng Shi district, kitchen component, needs to have the various characteristic such as water-repellancy, slipperiness that can tolerate harsher environment for use.
To this, the composition being reduced surface free energy by the little low surface free energy compound of compounding surface free energy has been attempted to coat component surface, good water-repellancy is given to component, dirt is not easily adhered to, as above-mentioned low surface free energy compound, use the hydrophobic material such as fluoro-resin, siloxane-based compound.
Such as, the following surface that Patent Document 1 discloses has paint solidification Wu Shi district component containing low surface free energy compound, and then, as low surface free energy compound, disclose silicone resin compound, fluoro-resin compound.
In addition, following Patent Document 2 discloses forms low surface free energy layer on substrate resin surface and makes molding surface and substrate resin surface be in a ratio of the resin molded body on low surface free energy surface, and then disclose, the surface of this resin molded body and the contact angle of water are more than 90 degree and less than 170 degree, and the surface of this resin molded body and the landing angle of water are more than 1 degree and less than 80 degree.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2002-69378 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2000-233156 publication
Summary of the invention
the problem that invention will solve
But, state before use low surface free energy compound make low surface free energy surface in the middle of, although water and the glomerate water droplet of shape are on a surface repelled in the surface using fluoro-resin compound to make, often find that this water droplet is strongly attached to and drop on the surface and not.On the other hand, even if initial landing angle, the surface using silicone resin compound to make is little, along with reusing, also have that smoothness of the surface reduces, landing angle becomes large tendency.Therefore, also attempted, by making surface roughening etc. make the contact angle on surface increase as much as possible, the water droplet of attachment being dropped from surface, but the surface of having carried out roughening etc. like this in weather resistance, dirt easily adhere in existing problems.
And then usually also there is the problem with the poor compatibility of matrix resin in low surface free energy compound as above.
Therefore, the object of the invention is to, in order to solve the problem, provide the Photocurable resin composition that can improve water-repellancy and slipperiness in for a long time.In addition, another object of the present invention be to provide have by the coating layer of above-mentioned Photocurable resin composition solidification, water-repellancy and the slipperiness good wet district component of maintenance and functional panel in long-time.
for the scheme of dealing with problems
The present inventor etc. conduct in-depth research to reach above-mentioned purpose, found that, (a) polysiloxane polyhydric alcohol (silicone polyol) is made by using (A) as the constituent of Photocurable resin composition, (b) isocyanic ester, (c) end has and can carry out reacting with (methyl) acrylate monomer of the functional group of isocyanate reaction and dimethyl siloxane (methyl) origoester acrylate obtained, good with the consistency of matrix resin, the sliding aqueous surface of the water droplet easily can removing surface can be formed, and can form that have can the overlay film of weather resistance that uses of withstand prolonged, thus complete the present invention.
It should be noted that, in this specification sheets, " (methyl) acrylate " represents acrylate or methacrylic ester.
In addition, the discoveries such as the present inventor, be greater than 100/100 by the equivalence ratio (-NCO/-OH) of the hydroxyl (-OH) in the isocyanate group (-NCO) in (b) isocyanic ester and (a) polysiloxane polyhydric alcohol is set to and is less than 300/100, the prepolymer that end has isocyanate group can be made, then, the isocyanate group of prepolymer end is reacted with the monomer such as with hydroxyl and (methyl) acryl, end can be made there is high dimethyl siloxane (methyl) origoester acrylate (dimethyl silicone(meth) the acrylate oligomer of the water-repellancy of (methyl) acryl), thus complete the present invention.
That is, the feature of Photocurable resin composition of the present invention is, contains:
(A) make the polysiloxane polyhydric alcohol shown in (a) following general formula (1), (b) isocyanic ester and (c) end have and can carry out reacting with (methyl) acrylate monomer of the functional group of isocyanate reaction and dimethyl siloxane (methyl) origoester acrylate obtained; Can with the copolymerization of aforementioned (A) dimethyl siloxane (methyl) origoester acrylate, (B) optical polymerism oligopolymer and/or (C) photopolymerization monomer; And (D) Photoepolymerizationinitiater initiater.
Wherein, in aforementioned formula (1), n represent with the number-average molecular weight of aforementioned (A) dimethyl siloxane (methyl) origoester acrylate be 700 ~ 40000 the optional integer of mode, R represents the alkylidene group of total carbon number 1 ~ 30 or has the functional group of total carbon number 1 ~ 30 of ehter bond.
In the preference of Photocurable resin composition of the present invention, the equivalence ratio (isocyanate group/hydroxyl) of the hydroxyl in the polysiloxane polyhydric alcohol shown in the isocyanate group in aforementioned (b) isocyanic ester and aforementioned (a) general formula (1) is greater than 100/100 and is less than 300/100.
In another preference of Photocurable resin composition of the present invention, the solubility parameter (SP value) of aforementioned (C) photopolymerization monomer is 20.0 (J/cm 3) 1/2below.
Wherein, aforementioned (C) photopolymerization monomer can be a kind of separately, also can combine two or more.Here, SP value during two or more photopolymerization monomer is used to refer to, the SP value had by each monomer is multiplied by each compounding ratio (mass ratio) (ratio of each monomer when monomer total amount being set to 1), the value obtained the summation of these products.Such as, relative to photopolymerization monomer total amount 1, during the photopolymerization monomer of the photopolymerization monomer of the compounding SP of the amount with 3/4 value 19.0, the compounding SP value 21.0 of amount with 1/4, obtain the SP value of used photopolymerization monomer entirety according to following formula (X).
SP value=(19.0 × 3/4)+(21.0 × 1/4)=19.5 (X) of photopolymerization monomer
In another preference of Photocurable resin composition of the present invention, aforementioned (C) photopolymerization monomer is the compound shown in following general formula (A).
(CH 2=CR 1cOO) nr 2general formula (A)
Wherein, in aforementioned formula (A), R 1represent hydrogen atom or methyl, R 2represent the alkyl of the n valency of carbon number 5 ~ 20, n represents the integer in the scope of 1 ~ 4.
In another preference of Photocurable resin composition of the present invention, aforementioned (B) optical polymerism oligopolymer is for having (methyl) origoester acrylate of 1,2-polyoxybutylene (1,2-polybutylene oxide) unit.
In another preference of Photocurable resin composition of the present invention, aforementioned (b) isocyanic ester is the polyisocyanate compound in molecular structure with cyclic skeleton.
In another preference of Photocurable resin composition of the present invention, in aforementioned (c) (methyl) acrylate monomer can be hydroxyl with the functional group of isocyanic ester radical reaction.
In another preference of Photocurable resin composition of the present invention, relative to the total of (B) optical polymerism oligopolymer and/or (C) photopolymerization monomer, the content of aforementioned (A) dimethyl siloxane (methyl) origoester acrylate is 0.05 quality % ~ 10 quality %.
In addition, the feature of wet district of the present invention component is to have: the coating layer solidified by Photocurable resin composition; And substrate layer.
In addition, the feature of functional panel of the present invention is to have: by the coating layer of Photocurable resin composition solidification of the present invention; And substrate layer.
the effect of invention
According to the present invention, can provide a kind of Photocurable resin composition, it comprises: (A) makes the polysiloxane polyhydric alcohol shown in (a) general formula (1), (b) isocyanic ester and (c) end have can to carry out reacting with (methyl) acrylate monomer of the functional group of isocyanate reaction and dimethyl siloxane (methyl) origoester acrylate obtained; (B) optical polymerism oligopolymer and/or (C) photopolymerization monomer; And (D) Photoepolymerizationinitiater initiater, described Photocurable resin composition can improve water-repellancy and slipperiness in long-time.In addition, can provide have by the coating layer of described Photocurable resin composition solidification, water-repellancy and slipperiness good wet district component and functional panel in long-time.
Embodiment
(Photocurable resin composition)
Below, the present invention is described in detail.Photocurable resin composition of the present invention contains: (A) dimethyl siloxane (methyl) origoester acrylate, (B) optical polymerism oligopolymer and/or (C) photopolymerization monomer and (D) Photoepolymerizationinitiater initiater, as required containing (E) other composition.
In Photocurable resin composition of the present invention, (A) dimethyl siloxane (methyl) origoester acrylate due to the surface energy at the dimethyl siloxane position of (a) polysiloxane polyhydric alcohol used as one of starting raw material low, therefore, it is possible to play a role as low surface free energy compound, such as, can improve there is the wet district component of the coating layer obtained by this Photocurable resin composition and the water-repellancy of functional panel and slipperiness.
In addition, in Photocurable resin composition of the present invention, (A) dimethyl siloxane (methyl) origoester acrylate is segregated on the surface in long-time, as its result, such as, raising the wet district component of the coating layer obtained by this Photocurable resin composition and the water-repellancy of functional panel and slipperiness can be had in long-time.
< (A) dimethyl siloxane (methyl) origoester acrylate >
(A) dimethyl siloxane (methyl) origoester acrylate used in Photocurable resin composition of the present invention makes (a) polysiloxane polyol component, (b) isocyanate prepolymer composition and (c) (methyl) acrylate monomer compositions carry out reacting and obtaining.Should such as can obtain as follows by (A) dimethyl siloxane (methyl) origoester acrylate: (a) polysiloxane polyhydric alcohol and (b) isocyanic ester are reacted, part or all of synthesizing end has the polysiloxane polyhydric alcohol prepolymer of isocyanate group, then, addition (c) (methyl) acrylate monomer in isocyanate group in this polysiloxane polyhydric alcohol prepolymer, thus obtain.
Dimethyl siloxane (methyl) origoester acrylate is obtained by using isocyanic ester, the prepolymer with any repeat number can be synthesized, the physics value (flexibility, intensity, cementability etc.) of oligopolymer that can adjust molecular weight thus or obtain, and the amino-formate bond that the polarity containing any number in molecule is high can be made, therefore, have and easily carry out the advantage with the Compatibility Design of matrix resin.
As the number-average molecular weight of aforementioned (A) dimethyl siloxane (methyl) origoester acrylate, be not particularly limited, suitably can select according to object, be preferably 1000 ~ 40000.Aforementioned number-average molecular weight with GPC by polystyrene standard production standard curve, can be obtained by the retention time of sample.The mobile phase solvent of GPC can use tetrahydrofuran (THF), chloroform.In addition, detector can use refractometer (RI), UV detector etc.When making the number-average molecular weight that obtains in this way less than 1000, (A) relative quantity at the dimethyl siloxane position in dimethyl siloxane (methyl) origoester acrylate reduces, therefore in order to play sufficient effect, need to increase addition.On the other hand, when number-average molecular weight is more than 40000, consistency with (B) the optical polymerism oligopolymer that can be polymerized with (A) dimethyl siloxane (methyl) origoester acrylate and/or (C) photopolymerization monomer obviously reduces and is separated, and due to cross-linking density reduction, therefore film surface becomes soft, forms the surface easily scratched.
(A) dimethyl siloxane (methyl) origoester acrylate except have containing the polysiloxane polyhydric alcohol shown in (a) general formula (1), (b) isocyanic ester, (c) end can with (methyl) acrylate monomer of the functional group of isocyanate reaction except, can also (d) other polyhydroxy reactant be contained.Now, by (a) polysiloxane polyhydric alcohol, (d) other polyvalent alcohol and the copolymerization of (b) isocyanic ester, part or all of synthesizing end has the polysiloxane polyhydric alcohol prepolymer of isocyanate group, then, in isocyanate group in this polysiloxane polyhydric alcohol prepolymer addition (c) end have can with (methyl) acrylate monomer of the functional group of isocyanate reaction, thus to obtain.
By containing (d) other polyhydroxy reactant, can at random adjust water-repellancy, with the consistency of matrix resin, the hardness etc. of cured article.
As the content of aforementioned (A) dimethyl siloxane (methyl) origoester acrylate, be not particularly limited, suitably can select according to object, relative to the total of (B) optical polymerism oligopolymer and/or (C) photopolymerization monomer, be preferably 0.05 quality % ~ 10 quality %, be more preferably 0.1 quality % ~ 5.0 quality %.Herein, the content of (A) dimethyl siloxane (methyl) origoester acrylate is the amount (amount of solids component) of the effective constituent of (A) dimethyl siloxane (methyl) origoester acrylate.
Aforementioned containing quantity not sufficient 0.05 quality % time, sometimes water-repellancy, the water skiing of the article being coated with Photocurable resin composition of the present invention cannot be improved fully, during more than 10 quality %, worsen with the consistency of (B) optical polymerism oligopolymer and/or (C) photopolymerization monomer, sometimes can not get uniform cured article.On the other hand, when the content of aforementioned (A) dimethyl siloxane (methyl) origoester acrylate is in aforementioned preferred scope, (A) surface segregation of dimethyl siloxane (methyl) origoester acrylate becomes more obvious, and the article being coated with Photocurable resin composition of the present invention can show water-repellancy water skiing within the longer time.In addition, additive effect is roughly saturated 5.0% time, and therefore, the content of (A) dimethyl siloxane (methyl) origoester acrylate being located at aforementioned preferred scope interior is also favourable from the viewpoint of cost.
-(a) polysiloxane polyhydric alcohol-
(a) polysiloxane polyhydric alcohol used as one of the starting raw material of aforementioned (A) dimethyl siloxane (methyl) origoester acrylate is represented by following general formula (1).
Wherein, in aforementioned formula (1), as long as n represent with the number-average molecular weight of aforementioned (A) dimethyl siloxane (methyl) origoester acrylate be 700 ~ 40000 mode (be the mode of 500 ~ 40000 with the number-average molecular weight of aforementioned polysiloxane polyhydric alcohol) optional integer, just be not particularly limited, suitably can select according to object.
In addition, in aforementioned formula (1), as R, as long as total for carbon number 1 ~ 30 alkylidene group or there is the functional group of total carbon number 1 ~ 30 of ehter bond, be just not particularly limited, suitably can select according to object.
As the alkylidene group of aforementioned total carbon number 1 ~ 30, be not particularly limited, suitably can select according to object, include, for example out methylene radical, ethylidene, propylidene, butylidene, pentylidene, hexylidene, sub-heptyl, the alkylidene group without total carbon number 1 ~ 30 of ehter bond such as octylene.
In addition, as the aforementioned functional group with total carbon number 1 ~ 30 of ehter bond, be not particularly limited, suitably can select according to object, include, for example out-C 3h 6-O-C 2h 4-,-C 3h 6-(OC 2h 4) m-: m is the integer ,-C that make total carbon number be no more than 30 2h 4-O-C 2h 4-,-C 3h 6-O-C 3h 6-etc.
Total carbon number of R being set to less than 30 is viewpoint for dimethyl siloxane (dimethyl silicone) concentration, thermotolerance etc.As R, from the view point of easily commercially obtaining, preferred propylidene or-C 3h 6-O-C 2h 4-.
And then, as an example of aforementioned formula (1), following general formula (2) can be listed.
Wherein, in aforementioned formula (2), n represent with the number-average molecular weight of aforementioned (A) dimethyl siloxane (methyl) origoester acrylate be 700 ~ 40000 mode (be the mode of 500 ~ 40000 with the number-average molecular weight of aforementioned polysiloxane polyhydric alcohol) optional integer, p represents the integer in the scope of 0 ~ 9, and q represents the integer in the scope of 3 ~ 9.
As the commercially available product of aforementioned (a) polysiloxane polyhydric alcohol, be not particularly limited, suitably can select according to object, (Gelest company manufactures: number-average molecular weight ≈ 700:p=0 to include, for example out DMS-C16, q=3), (CHISSO CORPORATION manufactures FM-4411: number-average molecular weight ≈ 1000:p=1, q=3), (CHISSO CORPORATION manufactures FM-4421: number-average molecular weight ≈ 5000:p=1, q=3), (CHISSO CORPORATION manufactures FM-4425: number-average molecular weight ≈ 10000:p=1, q=3), (Shin-Etsu Chemial Co., Ltd manufactures KF-6001: number-average molecular weight ≈ 1700:p=1, q=3), (Shin-Etsu Chemial Co., Ltd manufactures KF-6002: number-average molecular weight ≈ 3000:p=1, q=3), (Shin-Etsu Chemial Co., Ltd manufactures KF-6003: number-average molecular weight ≈ 5500:p=1, q=3), (Shin-Etsu Chemial Co., Ltd manufactures X-22-4952: number-average molecular weight ≈ 4000:p ≈ 5, q=3) etc.These can be used alone one, also can combinationally use two or more.
In aforementioned formula (2), p and q represents the integer in above-mentioned scope.By changing their length, can change the consistency with matrix resin, on the other hand, time long, the siloxane concentrations in structure relatively reduces, and therefore cannot play sufficient function.When p and q is in above-mentioned scope, does not affect as the water-repellancy of target of the present invention and the object of slipperiness (easily can remove the water skiing of surperficial water droplet) improving in long-time, function can be shown fully.
In addition, aforementioned (a) polysiloxane polyhydric alcohol such as can manufacture by utilizing platinum group catalyst to make the compound having hydroxyl and an alkenyl containing the dimethyl polysiloxane of end Si-H base and each end carry out addition reaction.
As the number-average molecular weight (Mn) of aforementioned (a) polysiloxane polyhydric alcohol, as long as be 500 ~ 20000, be just not particularly limited, suitably can select according to object.Aforementioned number-average molecular weight with GPC by polystyrene standard production standard curve, can be obtained by the retention time of sample.The mobile phase solvent of GPC can use tetrahydrofuran (THF), chloroform.In addition, detector can use refractometer (RI), UV detector etc.
When aforementioned number-average molecular weight is less than 500, the relative quantity at the dimethyl siloxane position in structure reduces, therefore in order to play sufficient effect, need to increase addition, during more than 20000, consistency with (B) the optical polymerism oligopolymer that can be polymerized with (A) dimethyl siloxane (methyl) origoester acrylate and/or (C) photopolymerization monomer obviously reduces and is separated, and due to cross-linking density reduction, therefore film surface becomes soft, forms the surface easily scratched.
-(b) isocyanic ester-
As (b) isocyanic ester of one of the starting raw material being used as aforementioned (A) dimethyl siloxane (methyl) origoester acrylate, be not particularly limited, suitably can select according to object, there is in preferred molecular structure the polyisocyanate compound of cyclic skeleton.
When aforementioned (b) isocyanic ester is the polyisocyanate compound in molecular structure with cyclic skeleton, (A) dimethyl siloxane (methyl) origoester acrylate self obtained by isocyanic ester also has cyclic skeleton in the molecular structure.The cyclic skeleton be present in the molecular structure of this (A) dimethyl siloxane (methyl) origoester acrylate forms steric hindrance, suppress (A) dimethyl siloxane (methyl) origoester acrylate to enter the inside of Photocurable resin composition, (A) dimethyl siloxane (methyl) origoester acrylate is segregated on the surface for a long time.
There is as aforementioned (b) isocyanic ester the polyisocyanate compound of cyclic skeleton in the molecular structure, as long as there is in molecular structure cyclic skeleton (cyclic moieties) and there is multiple isocyanate group (NCO yl), just be not particularly limited, suitably can select according to object, include, for example out naphthalene diisocyanate (NDI), tolylene diisocyanate (TDI), Xylene Diisocyanate (XDI), isophorone diisocyanate (IPDI), diphenylmethanediisocyanate (MDI), PPDI (PPDI), tolidine diisocyanate (TODI), dianisidine diisocyanate (DADI), dicyclohexyl methane diisocyanate (H12MDI), two (isocyanatomethyl) hexanaphthene (H6XDI) of 1,3-, tetramethylxylene diisocyanate (TMXDI), norbornylene vulcabond (NBDI), and comprise the NCO terminal carbamate ester prepolymer etc. of these structures.These can be used alone one, also can combinationally use two or more.
Wherein, preferred naphthalene diisocyanate (NDI), tolylene diisocyanate (TDI), Xylene Diisocyanate (XDI), isophorone diisocyanate (IPDI).
The consumption of aforementioned (a) polysiloxane polyhydric alcohol and (b) isocyanic ester can suitably change, the isocyanate group (-NCO) in (b) isocyanic ester and the equivalence ratio (-NCO/-OH) of the hydroxyl in (a) polysiloxane polyhydric alcohol be preferably greater than 100/100 and be less than 300/100 scope.
In addition, when synthesizing aforementioned (A) dimethyl siloxane (methyl) origoester acrylate, (b) isocyanic ester is reacted with the hydroxyl in (a) polysiloxane polyhydric alcohol, part or all of synthesis end when having the carbamate prepolymer of isocyanate group, makes the isocyanate group (-NCO) in (b) isocyanic ester be greater than 1 with the equivalence ratio (-NCO/-OH) of the hydroxyl in (a) polysiloxane polyhydric alcohol.
1 is greater than with the equivalence ratio (-NCO/-OH) of the hydroxyl in (a) polysiloxane polyhydric alcohol by making the isocyanate group (-NCO) in (b) isocyanic ester like this, can synthesize two ends is the prepolymer of isocyanate group, utilize this isocyanate group, can react with the functional group's (such as, isocyanate group) in (c) (methyl) acrylate monomer.
In the reaction of aforementioned (a) polysiloxane polyhydric alcohol with (b) isocyanic ester, preferably use the catalyzer of urethane reaction.
As the anti-applications catalyst of aforementioned urethane, be not particularly limited, suitably can select according to object, include, for example out the organo-tin compounds such as dibutyl tin laurate, dibutyltin diacetate, thiocarboxylic acid dibutyl tin, two dibutyitin maleate, thiocarboxylic acid dioctyl tin, octylenic acid tin, Mono-n-butyltin; The inorganic tin compounds such as tin protochloride; The organo-lead compounds such as octene lead plumbate; The cyclic amines such as triethylene diamine; The organic sulfonic acids such as tosic acid, methylsulfonic acid, fluosulfonic acid; The mineral acids such as sulfuric acid, phosphoric acid, perchloric acid; The bases such as sodium alkoxide, lithium hydroxide, aluminium alcoholates, sodium hydroxide; The titanium compounds such as tetrabutyl titanate, tetraethyl titanate, titanium isopropylate; Bismuth compound; Quaternary ammonium salt; Deng.These can be used alone one, also can combinationally use two or more.
Wherein, machine tin compound is preferably had.
As the consumption of the anti-applications catalyst of aforementioned urethane, be not particularly limited, suitably can select according to object, relative to 100 mass parts aforementioned (a) polysiloxane polyhydric alcohols, be preferably 0.001 mass parts ~ 2.0 mass parts.
-(c) (methyl) acrylate monomer-
As (c) (methyl) acrylate monomer of one of the starting raw material being used as aforementioned (A) dimethyl siloxane (methyl) origoester acrylate, as long as end contain can with the functional group of isocyanate reaction, just be not particularly limited, suitably can select according to object.
As aforementioned can with the functional group of isocyanate reaction, be not particularly limited, suitably can select according to object, include, for example out hydroxyl (-OH), carboxyl (-COOH), primary amino, secondary amino group etc.
Wherein, from reactive quality of aforementioned isocyanates, the abundant species of commercially available product and the aspect easily obtained, preferably hydroxyl.
As aforementioned (methyl) acrylate monomer with hydroxyl (-OH), be not particularly limited, suitably can select according to object, include, for example out (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 2-hydroxy butyl ester, (methyl) vinylformic acid 4-hydroxy butyl ester, (methyl) vinylformic acid 2-hydroxyl-3-phenoxy-propyl, (methyl) vinylformic acid 4-hydroxycyclohexyl, neopentyl glycol single (methyl) acrylate, TriMethylolPropane(TMP) two (methyl) acrylate, tetramethylolmethane three (methyl) acrylate etc.
As aforementioned (methyl) acrylate monomer with carboxyl (-COOH), be not particularly limited, suitably can select according to object, include, for example out succsinic acid 2-(methyl) acryloyloxyethyl ester, succsinic acid 2-acryloyloxyethyl ester, phthalic acid monohydroxy ethyl (methyl) acrylate etc.
As aforementioned, there is amino (methyl) acrylate monomer, be not particularly limited, suitably can select according to object, include, for example out (methyl) acrylate that side chain is 1-amino-ethyl, (methyl) acrylate etc. that side chain is 1-aminopropyl.
(c) (methyl) acrylate monomer also can in structure containing can with (methyl) acryl of the functional group of isocyanate reaction and optical polymerism.The quantity of aforementioned (methyl) acryl can be used for arbitrary (c) (methyl) acrylate monomer; quantity more (more multifunctional), (A) dimethyl siloxane (methyl) origoester acrylate is more multifunctional.Usually, functional group number is more, and (methyl) acrylate monomer is higher with the reactivity of (B) optical polymerism oligopolymer or (C) photopolymerization monomer, but when functional group number is too much, due to steric hindrance, reactivity reduces sometimes.Consider these aspects, the functional group number of (methyl) acrylate monomer is preferably between 2 ~ 10, in this range more preferably functional group number many (close to 10).In this range, functional group number is more, and being cross-linked of (methyl) acrylate monomer is denser, therefore, it is possible to segregation from the teeth outwards long-term and stably, and can improve surface hardness, so preferably.
Above-mentioned (c) (methyl) acrylate monomer can be used alone one, also can combinationally use two or more.
The consumption of above-mentioned (c) (methyl) acrylate monomer can suitably change, make the isocyanate group (-NCO) in the reaction product (carbamate prepolymer) formed relative to the polyisocyanate compound that there is cyclic skeleton in the molecular structure by (a) polysiloxane polyhydric alcohol and (b) isocyanic ester, can use more than 1 equivalent with the equivalent of the functional group of isocyanate reaction (functional group/-NCO) in (c) (methyl) acrylate monomer.
< (B) optical polymerism oligopolymer and/or (C) photopolymerization monomer >
(B) the optical polymerism oligopolymer used in Photocurable resin composition of the present invention and/or (C) photopolymerization monomer contain free-radical polymerised reactive group, such as (methyl) acryl [CH 2=CHCO-or CH 2=C (CH 3) CO-] etc.It should be noted that, in the present invention, from (B) optical polymerism oligopolymer, get rid of above-mentioned (A) dimethyl siloxane (methyl) origoester acrylate.
In addition, (B) optical polymerism oligopolymer is 100:0 ~ 0:100, preferably 80:20 ~ 20:80, the scope being more preferably 30:70 ~ 70:30 with the compounding amount of (C) photopolymerization monomer by quality ratio.(C) when the compounding amount of photopolymerization monomer is very few, the viscosity of the resin Photocurable composition obtained rises, and coating when worrying coating worsens, and possibly cannot guarantee the physical property such as chemical proofing and resistance to dyeability fully.In addition, when the compounding amount of photopolymerization monomer is too much, the flexibility existed when making film reduces and tendency that fragility uprises.
-(B) optical polymerism oligopolymer-
As aforementioned (B) optical polymerism oligopolymer, be not particularly limited, suitably can select according to object, preferably there is more than one acryloxy [CH 2=CHCOO-] or methacryloxy [CH 2=C (CH 3) COO-] and (methyl) origoester acrylate, particularly preferably there is (methyl) origoester acrylate of 1,2-polyoxybutylene unit.This has 1, (methyl) origoester acrylate of 2-polyoxybutylene unit due to polarity low, therefore good with the consistency of (A) dimethyl siloxane (methyl) origoester acrylate, (A) dimethyl siloxane (methyl) origoester acrylate can be added in wide region.Therefore, even if when the addition of (A) dimethyl siloxane (methyl) origoester acrylate is many, also gonorrhoea, layering etc. can be suppressed, the characteristic after solidification can be made even, and the outward appearance of film is good, use its wet district component and functional panel also can form good physical property and outward appearance.In addition, the hydrophobicity of resin Photocurable resin composition solidification obtained is high, therefore strong to the tolerance of the staining agents such as the clean-out system used in Shui Heshi district, hair dye, and dirt not easily adheres to, and the permanent stability of water skiing become better.
In addition, be low polarity about aforementioned (methyl) origoester acrylate (A), specifically, can represent by the value of normal heptane degree of accommodation (tolerance), above-mentioned value is preferably more than 0.5g/10g, is more preferably more than 0.7g/10g.It should be noted that, normal heptane accommodation degree refers to, 10g resin is remained on 25 DEG C, dripping normal heptane wherein, the value of the amount (g) of the normal heptane that can add till gonorrhoea on one side, is the deliquescent index to organic solvent, this value is larger, represents to be more low polarity.
As aforementioned (methyl) origoester acrylate, be not particularly limited, suitably can select according to object, include, for example out carbamate system (methyl) origoester acrylate, epoxy (methyl) origoester acrylate, ether system (methyl) origoester acrylate, ester system (methyl) origoester acrylate, polycarbonate-based (methyl) origoester acrylate, siloxane-based (methyl) origoester acrylate etc.These (methyl) origoester acrylates can be synthesized with (methyl) acrylic acid reaction by the affixture etc. of polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene ether diol, bisphenol A type epoxy resin, phenol novolak type epoxy resin, polyvalent alcohol and 6-caprolactone, or by making polyisocyanate compound synthesize with (methyl) acrylic compound urethane with hydroxyl.
Aforementioned (B) optical polymerism oligopolymer can be any number of in simple function oligopolymer, 2 functional oligomers, multifunctional oligopolymer, from the view point of the cross-linking density realizing the appropriateness of Photocurable resin composition obtained, be preferably multifunctional oligopolymer.
In the middle of aforementioned (B) optical polymerism oligopolymer, from the view point of giving the characteristic be suitable for as wet district's component and functional panel, carbamate system (methyl) origoester acrylate of preferred chemical proofing excellence.
Aforementioned carbamate system (methyl) origoester acrylate such as can manufacture as follows: by (i) polyvalent alcohol and (ii) polyisocyanates synthesis of carbamates prepolymer, to this carbamate prepolymer addition (iii) have can with the compound of the functional group of isocyanate reaction, (methyl) acrylate such as with hydroxyl, thus manufacture.
--(i) polyvalent alcohol--
The polyvalent alcohol used in synthesis as aforementioned carbamate prepolymer, as long as have the compound of multiple hydroxyl (-OH), just be not particularly limited, suitably can select according to object, include, for example out polyether glycol, polyester polyol, polytetramethylene glycol, polybutadiene polyol, oxirane modified polybutadiene polyvalent alcohol, polyisoprene polyol etc.These can be used alone one, also can combinationally use two or more.
Foregoing polyethers polyvalent alcohol can be obtained by addition polymerization, such as can obtain by making the oxiranes such as polyvalent alcohol addition of ethylene oxide, propylene oxide such as ethylene glycol, propylene glycol, glycerine, TriMethylolPropane(TMP), tetramethylolmethane, Sorbitol Powder, in addition, also polyether glycol can be obtained by ring-opening polymerization.As foregoing polyethers polyvalent alcohol, be not particularly limited, suitably can select according to object, include, for example out the polytetramethylene glycol (poly tetramethylene glycol) etc. obtained by the ring-opening polymerization of tetrahydrofuran (THF) (THF).
Foregoing polyester polyols can be obtained by addition polymerization, such as can by ethylene glycol, Diethylene Glycol, 1,4-butyleneglycol, 1, the polycarboxylic acids such as the polyvalent alcohols such as 6-hexylene glycol, propylene glycol, trimethylolethane, TriMethylolPropane(TMP) and hexanodioic acid, pentanedioic acid, succsinic acid, sebacic acid, pimelic acid, suberic acid obtain, in addition, also polyester polyol can be obtained by ring-opening polymerization.As foregoing polyester polyols, be not particularly limited, suitably can select according to object, include, for example out the lactone system polyester polyol etc. obtained by the ring-opening polymerization of 6-caprolactone.
By using butylene oxide ring modified polyalcohol as aforementioned (i) polyvalent alcohol, aforementioned (methyl) origoester acrylate with 1,2-polyoxybutylene unit can be manufactured.This butylene oxide ring modified polyalcohol makes polyvalent alcohol and 1 under the existence of alkaline catalysts, 2 ?butylene oxide ring (BO) carry out addition polymerization and the polyether glycol obtained.In addition, also can be except 1,2 ? also make other oxiranes such as propylene oxide (PO) carry out addition polymerization outside butylene oxide ring (BO) and the polyether glycol that obtains simultaneously.Now, 1,2 ?the ratio of butylene oxide ring (BO) and other oxirane take molar ratio computing as 20:80 ~ 100:0, to be preferably 50:50 ~ 100:0 be desirable.The number-average molecular weight obtained by GPC of these butylene oxide ring modified polyalcohols is generally 100 ~ 15000, is preferably 500 ~ 5000.
--(ii) polyisocyanates--
As aforementioned polyisocyanates, as long as have the compound of multiple isocyanate group (-NCO), just be not particularly limited, suitably can select according to object, include, for example out tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), thick diphenylmethanediisocyanate (crude MDI), isophorone diisocyanate (IPDI), hydrogenated diphenyl methane diisocyanate, hydrogenated tolylene diisocyanate, hexamethylene diisocyanate (HDI), their isocyanurate-modified thing, carbodiimide modified thing, glycol modification thing etc.These can be used alone one, also can combinationally use two or more.
--the anti-applications catalyst of urethane--
In the synthesis of aforementioned carbamate prepolymer, preferably use the catalyzer of urethane reaction.As the anti-applications catalyst of aforementioned urethane, be not particularly limited, suitably can select according to object, include, for example out the organo-tin compounds such as dibutyl tin laurate, dibutyltin diacetate, thiocarboxylic acid dibutyl tin, two dibutyitin maleate, thiocarboxylic acid dioctyl tin, octylenic acid tin, Mono-n-butyltin; The inorganic tin compounds such as tin protochloride; The organo-lead compounds such as octene lead plumbate; The cyclic amines such as triethylene diamine; The organic sulfonic acids such as tosic acid, methylsulfonic acid, fluosulfonic acid; The mineral acids such as sulfuric acid, phosphoric acid, perchloric acid; The bases such as sodium alkoxide, lithium hydroxide, aluminium alcoholates, sodium hydroxide; The titanium compounds such as tetrabutyl titanate, tetraethyl titanate, titanium isopropylate; Bismuth compound; Quaternary ammonium salt; Deng.These can be used alone one, also can combinationally use two or more.
Wherein, machine tin compound is preferably had.
As the consumption of the anti-applications catalyst of aforementioned urethane, be not particularly limited, suitably can select according to object, relative to 100 mass parts aforementioned (i) polyvalent alcohols, be preferably 0.001 mass parts ~ 2.0 mass parts.
--(iii) have can with the compound of the functional group of isocyanate reaction--
In addition, having with (iii) of carbamate prepolymer addition can be have more than one to have with the functional group of isocyanate reaction (such as, hydroxyl) functional group ((methyl) acryloxy [CH that more than shows optical polymerism with the compound of the functional group of isocyanate reaction 2=CHCOO-or CH 2=C (CH 3) COO-]) compound.
Aforementioned (iii) has can with the isocyanate group addition in aforementioned carbamate prepolymer with the compound of the functional group of isocyanate reaction.
As aforementioned (iii) have can with the compound of the functional group of isocyanate reaction, be not particularly limited, suitably can select according to object, include, for example out (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, tetramethylolmethane three (methyl) acrylate, 2-hydroxyethyl vinylethers, diethylene glycol monovinyl base ether, 4-hydroxy butyl vinyl ether, 3-ethyl-3-hydroxymethyl-oxetane, succsinic acid 2-(methyl) acryloyloxyethyl ester, phthalic acid list hydroxyethyl (methyl) acrylate, side chain is (methyl) acrylate of 1-amino-ethyl, side chain is (methyl) acrylate etc. of 1-aminopropyl.These can be used alone one, also can combinationally use two or more.
By compounding this (B) optical polymerism oligopolymer, the second-order transition temperature that the coating layer that obtains shows by Photocurable resin composition solidification can be optimized, the Photocurable resin composition of the effect that can play water-repellancy and slipperiness excellence can be obtained.
-(C) photopolymerization monomer-
As aforementioned (C) photopolymerization monomer, be not particularly limited, suitably can select according to object, preferably there is more than one (methyl) acryloxy [CH 2=CHCOO-or CH 2=C (CH 3) COO-] and (methyl) acrylate monomer, can be any number of in functional monomer and (iii) multi-functional monomer of (i) mono-functional monomer, (ii) 2.
It should be noted that, aforementioned (C) photopolymerization monomer can be a kind of separately, also can be that combination is two or more.Here, SP value during two or more photopolymerization monomer is used to refer to, the SP value had by each monomer is multiplied by each compounding molar ratio (mass ratio) (ratio of each monomer when monomer total amount being set to 1), the value obtained the summation of these products.Such as, relative to photopolymerization monomer total amount 1, during the photopolymerization monomer of the photopolymerization monomer of the compounding SP of the amount with 3/4 value 19.0, the compounding SP value 21.0 of amount with 1/4, obtain the SP value of used photopolymerization monomer entirety according to following formula (X).
SP value=(19.0 × 3/4)+(21.0 × 1/4)=19.5 (X) of photopolymerization monomer
-(i) mono-functional monomer-
As aforementioned (i) mono-functional monomer, be not particularly limited, suitably can select according to object, include, for example out (methyl) isobornyl acrylate, (methyl) vinylformic acid norbornene ester, (methyl) vinylformic acid three ring decyl ester, (methyl) vinylformic acid bicyclopentyl ester, (methyl) vinylformic acid dicyclopentenyl ester, (methyl) cyclohexyl acrylate, (methyl) benzyl acrylate, (methyl) vinylformic acid 4-butylcyclohexyl ester, (methyl) acryloyl morpholine, (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 2-hydroxy butyl ester, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) isoamyl acrylate, (methyl) Ethyl acrylate, (methyl) heptylacrylate, (methyl) Octyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) 2-EHA, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) vinylformic acid undecyl ester, (methyl) dodecylacrylate, (methyl) lauryl acrylate, (methyl) stearyl acrylate base ester, (methyl) myristyl base ester, (methyl) vinylformic acid palmityl ester, (methyl) vinylformic acid iso stearyl ester, (methyl) vinylformic acid tetrahydro furfuryl ester, (methyl) acrylate, butoxy ethyl, ethoxydiglycol (methyl) acrylate, ethylene nonyl phenyl ether acrylate, (methyl) acrylate, polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate, methoxyl group ethylene glycol (methyl) acrylate, (methyl) ethoxyethyl acrylate, methoxy poly (ethylene glycol) (methyl) acrylate, methoxyl group polypropylene glycol (methyl) acrylate, (methyl) acrylate, (methyl) vinylformic acid diethylamino ethyl ester, amino-3, the 7-dimethyl monooctyl esters of (methyl) vinylformic acid 7-etc.These can be used alone one, also can combinationally use two or more.
-(ii) 2 functional monomer-
As aforementioned (ii) 2 functional monomer, be not particularly limited, suitably can select according to object, include, for example out ethylene glycol bisthioglycolate (methyl) acrylate, TEG two (methyl) acrylate, triethylene glycol two (methyl) acrylate, 1, 4-butyleneglycol two (methyl) acrylate, 1, 6-hexylene glycol two (methyl) acrylate, 1, 9-nonanediol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, three (2-hydroxyethyl) isocyanuric acid ester two (methyl) acrylate, Tricyclodecane Dimethanol two (methyl) acrylate, dihydroxymethyl tristane two (methyl) acrylate, two (methyl) acrylate of the oxirane addition glycol of dihydroxyphenyl propane, two (methyl) acrylate of the oxirane addition glycol of Hydrogenated Bisphenol A, make the diglycidylether of dihydroxyphenyl propane and (methyl) acrylate addition and epoxy (methyl) acrylate etc. that obtains.These can be used alone one, also can combinationally use two or more.
-the multi-functional monomer of (iii)-
As aforementioned (iii) multi-functional monomer, be not particularly limited, suitably can select according to object, include, for example out trimethylolpropane tris (methyl) acrylate, ethoxylated trimethylolpropane three (methyl) acrylate, propoxylation trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, two TriMethylolPropane(TMP) four (methyl) acrylate, Dipentaerythritol monohydroxy five (methyl) acrylate etc.These can be used alone one, also can combinationally use two or more.
As the solubility parameter (SP value) of foregoing photo-polymerization monomer, be not particularly limited, suitably can select according to object, be preferably 20.0 (J/cm 3) 0.5below, 19.6 (J/cm are more preferably 3) 0.5below.In addition, as the lower value of aforementioned SP value, be not particularly limited, be usually preferably 17.0 (J/cm 3) 0.5above.By making SP value low, improving with the consistency of (A) dimethyl siloxane (methyl) origoester acrylate, (A) dimethyl siloxane (methyl) origoester acrylate can be added in wide region.Therefore, even if when the addition of (A) dimethyl siloxane (methyl) origoester acrylate is many, also can suppress gonorrhoea, layering etc., the outward appearance after solidification is good, uses its wet district component and functional panel also can form good outward appearance.
Herein, SP value (δ) usually by liquid molar energy of vaporization (Δ Ev) and molecular volume (V), utilize following formula to define.
SP value (δ)=(Δ Ev/V) 0.5
And then SP value only can calculate (with reference to " dissolving パ ラ メ ー タ ー value (Solubility Parameter Values by chemical structure according to Fedors method; Solubility parameter value) ", " Port リ マ ー Ha Application De Block ッ Network " (Polymer Handbook; Polymer handbook), the 4th edition (J.Brandrup etc. write)).It should be noted that, in present disclosure, SP value refers to the value calculated by Fedors method, and this value is lower, represents that photopolymerization monomer (C) is more low polarity.
In addition, as aforementioned (C) photopolymerization monomer, the monomer shown in preferred following general formula (A).
(CH 2=CR 1cOO) nr 2general formula (A)
In general formula (A), R 1for hydrogen atom or methyl, R 2for the alkyl of the n valency of carbon number 5 ~ 20, not containing heteroatoms, can be chain also can be ring-type.In addition ,-the CH in group 2-also can replace with-CH=CH-.N is the integer of 1 ~ 4.
That is, in general formula (A), be such as chain and for saturated monomer time, R during n=1 2for the alkyl of carbon number 5 ~ 20, R during n=2 2for the alkylidene group of carbon number 5 ~ 20.And then, for chain and be saturated monomer time, R during n=3 2for alkane three base (alkantriyl group) of carbon number 5 ~ 20, R during n=4 2for alkane four base (alkanetetrayl group) of carbon number 5 ~ 20.As this R 2, such as, have-CH 2cH 3,-CH 2cH 2cH 3,-CH (CH 3) CH 3, cyclohexyl, suberyl, ring octyl group, ring nonyl, the alkyl such as ring decyl;-CH 2cH 2-,-CH 2cH 2cH 2-,-CH (CH 3) CH 2-wait alkylidene group; As CH 3cH 2c (CH 2-) 3shown in such alkane three base, as C (CH 2-) 4shown such alkane four base etc.
R 2carbon number less than 5 time, when the alkyl of chain, the tendency that the SP value that there is monomer rises, reduces with the consistency of (A) dimethyl siloxane (methyl) origoester acrylate, when the alkyl of ring-type, self be difficult to obtain.In addition, R 2carbon number more than 20 time, there is the tendency that the cross-linking density of Photocurable resin composition that obtains reduces.Reduce necessarily if cross-linking density exceeds, then the staining agent such as hair dye easily invades coating layer inside, therefore there is the worry that plate is colored.
As the object lesson of the monomer shown in general formula (A), include, for example out (methyl) isobornyl acrylate, 1, 6-hexylene glycol two (methyl) acrylate, dihydroxymethyl tristane two (methyl) acrylate, (methyl) isoamyl acrylate, (methyl) lauryl acrylate, (methyl) tridecyl acrylate, the different myristyl ester of (methyl) vinylformic acid, (methyl) stearyl acrylate base ester, 3-methyl isophthalic acid, 5-pentanediol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, cyclohexanedimethanol two (methyl) acrylate, 1, 9-nonanediol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, tetramethylolmethane four (methyl) acrylate etc.
Wherein, there is the tendency showing good low polarity owing to having SP value preferably, from improving the consistency with (A) dimethyl siloxane (methyl) origoester acrylate further, and chemical proofing, resistance to chromatic viewpoint is set out, preferably 1, 9-nonanediol two (methyl) acrylate, 1, 6-hexylene glycol two (methyl) acrylate, (methyl) isobornyl acrylate, dihydroxymethyl tristane two (methyl) acrylate, more preferably 1, 6-hexylene glycol two (methyl) acrylate, (methyl) isobornyl acrylate, 1, 9-nonanediol two (methyl) acrylate.
Aforementioned solubility parameter (SP value) is 20.0 (J/cm 3) 0.5monomer shown in following photopolymerization monomer, especially general formula (A) due to polarity low, therefore good with the consistency of (A) dimethyl siloxane (methyl) origoester acrylate, (A) dimethyl siloxane (methyl) origoester acrylate can be added in wide region.Therefore, even if when the addition of (A) dimethyl siloxane (methyl) origoester acrylate is many, also can suppress gonorrhoea, layering etc., the outward appearance after solidification is good, uses its wet district component and functional panel also can form good outward appearance.In addition, the hydrophobicity of resin Photocurable resin composition solidification obtained is high, therefore strong to the tolerance of the staining agents such as the clean-out system used in Shui Heshi district, hair dye, and dirt not easily adheres to, and the permanent stability of water skiing become better.
In addition, the functional group number of foregoing photo-polymerization monomer is generally 1 ~ 6, is preferably 1 ~ 4.It should be noted that, when functional group number is 1, to there is the tendency that cross-linking density reduces, but by using the monomer of cyclic skeleton, thus second-order transition temperature uprises, and can keep good film physical property.In addition, when functional group number is 2 ~ 6, preferably 2 ~ 4, existence moderately can keep the tendency of the crosslinking reaction of Photocurable resin composition, therefore can infer the phenomenon easily more effectively suppressing the particularly inner Er Shishi district component of staining agent intrusion coating layer and functional panel to be colored.Therefore, now also the wet district component and the functional panel that obtain being formed with the coating layer with suitable solidified nature under good didirtresistance and chemical proofing, resistance to chromatic prerequisite can effectively kept.
(B) optical polymerism oligopolymer and (C) photopolymerization monomer can only use oligopolymer, only use monomer, but preferably oligopolymer and combination of monomers are used.
< (D) Photoepolymerizationinitiater initiater >
(D) Photoepolymerizationinitiater initiater used in Photocurable resin composition of the present invention has the effect being caused the polymerization of above-mentioned (A) dimethyl siloxane (methyl) origoester acrylate, (B) optical polymerism oligopolymer and/or (C) photopolymerization monomer by light such as irradiation ultraviolet radiations.
As aforementioned (D) Photoepolymerizationinitiater initiater, be not particularly limited, suitably can select according to object, include, for example out 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid ester, 2,2-dimethoxy-2-phenyl acetophenone, methyl phenyl ketone diethyl ketal, alkoxy benzene ethyl ketone, benzil dimethyl ketal, benzophenone and 3,3-dimethyl-4-methoxy benzophenone, 4,4-dimethoxy-benzophenone, the benzophenone derivates such as 4,4-diaminobenzophenone, Benzoylbenzene alkyl formate, two (4-dialkylaminophenyl) ketone, the benzil derivatives such as benzil and benzil methyl ketal, the benzoin derivatives such as bitter almond oil camphor and benzoin isobutyl ether, benzoin iso-propylether, 2-hydroxy-2-methyl Propiophenone, 1-hydroxy-cyciohexyl-benzophenone, xanthone, thioxanthone and thioxanthone derivates, fluorenes, TMDPO, two (2,6-Dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, two (2,4,6-trimethylbenzoyl)-phenyl phosphine oxide, 2-methyl isophthalic acid-(4-methylthiophenyi)-2-morpholino propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl)-butanone-1 etc.These can be used alone one, also can combinationally use two or more.
As the compounding amount of aforementioned (D) Photoepolymerizationinitiater initiater in Photocurable resin composition of the present invention, be not particularly limited, suitably can select according to object, relative to total 100 mass parts of (A) dimethyl siloxane (methyl) origoester acrylate and (B) optical polymerism oligopolymer and/or (C) photopolymerization monomer, be preferably the scope of 0.1 mass parts ~ 10 mass parts.When the compounding amount of aforementioned (D) Photoepolymerizationinitiater initiater is more than 0.1 mass parts, can initiated polymerization fully, on the other hand, during more than 10 mass parts, the effect of initiated polymerization is saturated, on the other hand, paintedly become obvious, and the cost of the raw material of Photocurable resin composition uprises.
< (E) other composition >
-photosensitizers-
In Photocurable resin composition of the present invention, consider required solidification reactivity, stability etc., can also as required further containing photosensitizers.This photosensitizers has by irradiating light and absorbs energy, the effect of this energy or the transfer transport initiated polymerization to polymerization starter.As this photosensitizers, ESCAROL 507 isopentyl ester etc. can be listed.The compounding amount of these photosensitizerss, relative to total 100 mass parts of (A) optical polymerism siloxane oligomer and (B) optical polymerism oligopolymer and/or (C) photopolymerization monomer, is preferably the scope of 0.1 mass parts ~ 10 mass parts.
-stopper-
And then, in Photocurable resin composition of the present invention, consider required solidification reactivity, stability etc., stopper can also be contained as required.As this stopper, quinhydrones, hydroquinone monomethyl ether, p methoxy phenol, 2 can be listed, 4-dimethyl-6-tert.-butyl phenol, 2,6-di-t-butyls-p-cresol, butyl hydroxyanisole, 3-hydroxythiophenol, alpha-nitroso-beta-naphthol, para benzoquinone, 2,5-dihydroxyl-para benzoquinone etc.The compounding amount of these stoppers, relative to total 100 mass parts of (A) dimethyl siloxane (methyl) origoester acrylate and (B) optical polymerism oligopolymer and/or (C) photopolymerization monomer, is preferably the scope of 0.1 mass parts ~ 10 mass parts.
-organic solvent-
In addition, Photocurable resin composition of the present invention can also contain the organic solvents such as ether, ketone, ester as diluting solvent, as this organic solvent, propylene glycol methyl ether acetate (PMA), methylethylketone (MEK), methyl iso-butyl ketone (MIBK) (MIBK), acetone, n-Butyl lactate etc. can be listed.These diluting solvents can be used alone one, also can combinationally use two or more.
Photocurable resin composition of the present invention can use diluting solvent as described above as required, make coating aqueous, be applied to the surface on base material.As the method for coating, be not particularly limited, known method can be adopted, include, for example out intaglio plate coating, roller coat, reverse coating, cutter painting, mould painting, lip coating, scraper for coating, extrusion coated, ramp type coating (slide coating), the coating of line rod, heavy curtain coating, extrusion coated, spin coating etc.
(wet district component)
The feature of aforementioned wet district component is to have: by the coating layer of Photocurable composition solidification of the present invention; And substrate layer.Aforementioned wet district component is the component of the water repellency needing surface.As aforementioned wet district component, be not particularly limited, suitably can select according to object, include, for example out kitchen basin, materials for wall for kitchen use, wash stand, bathroom materials for wall, bathtub, bathroom ceiling material, bathroom floor panel material, bathroom table top, toilet, water tank etc.
(functional panel)
Functional panel of the present invention has the coating layer of Photocurable resin composition solidification of the present invention and substrate layer, and such as, preferably this coating layer is formed on this substrate layer.
As the thickness of functional panel entirety of the present invention, be not particularly limited, suitably can select according to object, be usually preferably more than 2.5mm.In addition, as the upper limit of the thickness of functional panel entirety of the present invention, be not particularly limited, suitably can select according to object.Aforementioned coating layer can be formed on both the front and backs on substrate layer, the basis that also can be formed in these substrate layers and coating layer as required be formed with between, the layers the multilayered structure in the middle layer formed by various material.Now, aforementioned coating layer has excellent water-repellancy and slipperiness as mentioned above, and it is desirable for therefore being formed as the outmost surface layer of functional panel by aforementioned coating layer.As aforementioned middle layer, being not particularly limited, suitably can selecting according to object, include, for example out the undercoat of the cementability for improving substrate layer and coating layer, for improving the ornament layer etc. imparting pattern, color of the designability of functional panel.
The functional panel of the present invention so obtained owing to being formed with aforementioned coating layer on substrate layer, therefore there is excellent water-repellancy and slipperiness, and wear resistant, chemical proofing, heatproof water-based and resistance to dyeability are also excellent, effectively suppress the attachment of the various dirts taking incrustation scale as representative, even if use containing the strong clean-out system of the pungency of acid, alkali, also not easily produce rotten, deteriorated.In addition, even if the staining agent using hair dye such, also variable color, dyeing is not easily produced.Therefore, the suitable especially functional panel as the bathroom or kitchen that are configured at premises of functional panel of the present invention.
< coating layer >
Can Photocurable resin composition of the present invention be applied on base material, then make its photocuring, thus form coating layer on substrate layer.As the method for carrying out photocuring, usually there is the method for the light such as irradiation ultraviolet radiation.The face formed on the substrate layer of coating layer can be the only face in the middle of front and back, also can be these two faces, suitably select as required.In addition, be not particularly limited by the irradiation dose of light during Photocurable resin composition solidification of the present invention, suitably can select according to object, when adopting ultraviolet, be generally exposure intensity 20mW/cm 2~ 2000mW/cm 2, irradiation dose 100mJ/cm 2~ 5000mJ/cm 2, thus, Photocurable resin composition of the present invention solidified usually in several seconds ~ tens seconds.Owing to being cured so at short notice, therefore, it is possible to realize the raising of the productivity of the functional panel obtained.
As the thickness of aforementioned coating layer, be not particularly limited, suitably can be selected according to object by the level of required designability, chemical proofing, be usually assumed to the thickness of the scope of 1 μm ~ 200 μm.
In addition, during irradiation ultraviolet radiation, ultraviolet curing reaction is free radical reaction, is therefore easily subject to the obstruction caused by oxygen.Therefore, aforementioned Photocurable resin composition is applied to after on base material, in order to avoid the contact with oxygen, also can in a nitrogen atmosphere said composition be solidified.In addition, the surface free energy of the coating layer formed by carrying out photocuring, from the view point of guaranteeing good water-repellancy and slipperiness fully, is generally 12mJ/m 2~ 30mJ/m 2desirable.
< substrate layer >
As the material of the substrate layer used in functional panel of the present invention, be not particularly limited, suitably can select according to object, include, for example out the inorganic materials such as slabstone (slate), concrete, metal, Calucium Silicate powder, calcium carbonate, glass; Wood materials; The organic materialss such as polypropylene, polystyrene, polycarbonate, unsaturated polyester resin; Their matrix material; Deng.
Wherein, preferably in organic materials, the material of the fiber such as glass fibre, carbon fiber, so-called FRP (fibre reinforced plastics) is added with.As aforementioned FRP, be not particularly limited, suitably can select according to object, include, for example out the sheet molding compound (SMC of the sheet comprising unsaturated polyester resin, weighting agent and glass fibre or carbon fiber; Sheet molding compound), be the bulk molding compound (BMC comprising the bulk of staple fibre of the matrix material same with SMC; Bulk molding compound) etc.Aforementioned FRP normally obtains compounding to heat-curing resin, organo-peroxide (solidifying agent), weighting agent, shrinking agent, internal mold release, reinforcement material, linking agent and thickening material etc., it, by putting into the mould that is set as specified temperature and pressurizeing, is configured as the shape corresponding to the place configured as building materials and uses.Wherein, if comprise as the unsaturated polyester of heat-curing resin, weighting agent and as the glass fibre of reinforcement material or the FRP of carbon fiber, then the intensity and weather resistance etc. of the functional panel entirety obtained can be improved further.
Aforementioned unsaturated polyester is generated by polyvalent alcohols such as the polyunsaturated polycarboxylic acid such as maleic anhydride, fumaric acid and ethylene glycol, propylene glycol, Diethylene Glycol, dipropylene glycol, 1,3-PD, neopentyl glycol, neopentyl glycol, trimethyl propane mono allyl ether, A Hydrogenated Bisphenol A, bis-phenol dioxy propyl ethers (bisphenol dioxypropyl ether).
As aforementioned weighting agent, be not particularly limited, suitably can select according to object, include, for example out calcium carbonate, aluminium hydroxide etc.Wherein, reduce from the view point of cost, preferred calcium carbonate, from the view point of the chemical proofing improving FRP self, preferred aluminium hydroxide.But, as mentioned above, when forming aforementioned coating layer, as base material, use calcium carbonate as the FRP of weighting agent even if adopt, also can improve the chemical proofing of functional panel entirety fully, therefore, it is possible to easily realize the functional panel with the substrate layer formed by the FRP of low cost.
About as the glass fibre of aforementioned reinforcement material and carbon fiber, be not particularly limited, suitably can select according to object, be suitable for using the fiber that staple length is about 20mm ~ 50mm, Fibre diameter is 5 μm ~ about 25 μm, in FRP with the amount of 10 quality % ~ 70 quality % containing being desirable.These compositions mix by the aforementioned FRP being used as substrate layer, manufacture have the thickness of regulation and the FRP of size with FRP manufacturing installation etc.
In addition, as the thickness of aforementioned substrates layer, be not particularly limited, can change according to the purposes of functional panel, be generally more than 2.5mm.As the upper limit of the thickness of aforementioned substrates layer, be not particularly limited, suitably can select according to object.
Embodiment
Below, enumerate embodiment and illustrate in greater detail the present invention, but the present invention is not by any restriction of following embodiment.
< Production Example 1>
By polysiloxane polyhydric alcohol (the SILAPLANE FM-4411 of 0.1mol number-average molecular weight 1000, general formula (2), p=1, q=3, (total carbon number 5 of the R in general formula (1)), CHISSO CORPORATION manufactures), the polyoxyethylene glycol (PEG#1000, Japan Oil Co) of 0.1mol number-average molecular weight 1000 and 0.06g dibutyl tin laurate to join in reaction vessel and to stir.Then, 0.3mol isophorone diisocyanate (VESTANAT IPDI, Evonik Degussa GmbH manufactures) is at room temperature added.Be heated 70 DEG C, make it react 2.5 hours at 300 rpm, obtain carbamate prepolymer solution.0.2mol pentaerythritol triacrylate (PE-3A is added in the pre-polymer solution total amount obtained, Kyoeisha Chemical Co., Ltd. manufactures), further stirring 4 hours, reaction is terminated, obtains dimethyl siloxane (methyl) origoester acrylate of number-average molecular weight about 3000.
< Production Example 2>
In Production Example 1, use the polysiloxane polyhydric alcohol (DMS-C16 of number-average molecular weight about 700, general formula (2), p=0, q=3, (total carbon number 3 of the R in general formula (1)), Gelest company manufactures) replace polysiloxane polyhydric alcohol (the SILAPLANE FM-4411 using number-average molecular weight 1000, general formula (2), p=1, q=3, (total carbon number 5 of the R in general formula (1)), CHISSO CORPORATION manufactures), in addition, to operate equally with Production Example 1, obtain dimethyl siloxane (methyl) origoester acrylate of number-average molecular weight about 3000.
< Production Example 3>
In Production Example 1, use the polysiloxane polyhydric alcohol (FM-4421 of number-average molecular weight about 5000, general formula (2), p=1, q=3, (total carbon number 5 of the R in general formula (1)), CHISSO CORPORATION manufactures) replace polysiloxane polyhydric alcohol (the SILAPLANE FM-4411 using number-average molecular weight 1000, general formula (2), p=1, q=3, (total carbon number 5 of the R in general formula (1)), CHISSO CORPORATION manufactures), in addition, to operate equally with Production Example 1, obtain dimethyl siloxane (methyl) origoester acrylate of number-average molecular weight about 7000.
< Production Example 4>
In Production Example 1, use the polysiloxane polyhydric alcohol (FM-4425 of number-average molecular weight about 10000, general formula (2), p=1, q=3, (total carbon number 5 of the R in general formula (1)), CHISSO CORPORATION manufactures) replace polysiloxane polyhydric alcohol (the SILAPLANE FM-4411 using number-average molecular weight 1000, general formula (2), p=1, q=3, (total carbon number 5 of the R in general formula (1)), CHISSO CORPORATION manufactures), in addition, to operate equally with Production Example 1, obtain dimethyl siloxane (methyl) origoester acrylate of number-average molecular weight about 12000.
< Production Example 5>
In Production Example 1, use the polysiloxane polyhydric alcohol (KF6001 of number-average molecular weight about 1700, general formula (2), p=1, q=3, (total carbon number 5 of the R in general formula (1)), Shin-Etsu Chemial Co., Ltd manufactures) replace polysiloxane polyhydric alcohol (the SILAPLANE FM-4411 using number-average molecular weight 1000, general formula (2), p=1, q=3, (total carbon number 5 of the R in general formula (1)), CHISSO CORPORATION manufactures), in addition, to operate equally with Production Example 1, obtain dimethyl siloxane (methyl) origoester acrylate of number-average molecular weight about 4000.
< Production Example 6>
In Production Example 1, use the polysiloxane polyhydric alcohol (KF6002 of number-average molecular weight about 3000, general formula (2), p=1, q=3, (total carbon number 5 of the R in general formula (1)), Shin-Etsu Chemial Co., Ltd manufactures) replace polysiloxane polyhydric alcohol (the SILAPLANE FM-4411 using number-average molecular weight 1000, general formula (2), p=1, q=3, (total carbon number 5 of the R in general formula (1)), CHISSO CORPORATION manufactures), in addition, to operate equally with Production Example 1, obtain dimethyl siloxane (methyl) origoester acrylate of number-average molecular weight about 5000.
< Production Example 7>
In Production Example 1, use the polysiloxane polyhydric alcohol (KF6003 of number-average molecular weight about 5500, general formula (2), p=1, q=3, (total carbon number 5 of the R in general formula (1)), Shin-Etsu Chemial Co., Ltd manufactures) replace polysiloxane polyhydric alcohol (the SILAPLANE FM-4411 using number-average molecular weight 1000, general formula (2), p=1, q=3, (total carbon number 5 of the R in general formula (1)), CHISSO CORPORATION manufactures), in addition, to operate equally with Production Example 1, obtain dimethyl siloxane (methyl) origoester acrylate of number-average molecular weight about 7500.
< Production Example 8>
In Production Example 1, use the polysiloxane polyhydric alcohol (X-22-4952 of number-average molecular weight about 4000, general formula (2), p ≈ 5, q=3, (total carbon number ≈ 13 of the R in general formula (1)), Shin-Etsu Chemial Co., Ltd manufactures) replace polysiloxane polyhydric alcohol (the SILAPLANE FM-4411 using number-average molecular weight 1000, general formula (2), p=1, q=3, (total carbon number 5 of the R in general formula (1)), CHISSO CORPORATION manufactures), in addition, to operate equally with Production Example 1, obtain dimethyl siloxane (methyl) origoester acrylate of number-average molecular weight about 6000.
< Production Example 9>
In Production Example 1, add vinylformic acid 2-hydroxyl ethyl ester (trade(brand)name: LIGHT-ESTER HOA, Kyoeisha Chemical Co., Ltd. manufactures) replace adding pentaerythritol triacrylate (PE-3A, Kyoeisha Chemical Co., Ltd. manufactures), in addition, to operate equally with Production Example 1, obtain dimethyl siloxane (methyl) origoester acrylate of number-average molecular weight about 3000.
< Production Example 10>
In Production Example 1, add dipropylene glycol acrylate (trade(brand)name: DPGA, Di-ichi Kogyo Seiyaku Co., Ltd. manufactures) replace adding pentaerythritol triacrylate (PE-3A, Kyoeisha Chemical Co., Ltd. manufactures), in addition, to operate equally with Production Example 1, obtain dimethyl siloxane (methyl) origoester acrylate of number-average molecular weight about 3000.
< Production Example 11>
In Production Example 1, add succsinic acid 2-acryloyloxyethyl ester (trade(brand)name: chemical industry society of A-SA, Xin Zhong village manufactures) to replace adding pentaerythritol triacrylate (PE-3A, Kyoeisha Chemical Co., Ltd. manufactures), in addition, to operate equally with Production Example 1, obtain dimethyl siloxane (methyl) origoester acrylate of number-average molecular weight about 3000.
< Production Example 12>
In Production Example 1, the hexamethylene diisocyanate (trade(brand)name: HDI, Evonik Degussa manufactures) added as the polyisocyanate compound in molecular structure without cyclic skeleton replaces adding isophorone diisocyanate (VESTANAT IPDI, Evonik Degussa GmbH manufactures), in addition, to operate equally with Production Example 1, obtain dimethyl siloxane (methyl) origoester acrylate of number-average molecular weight about 3000.
< Production Example 13>
In Production Example 1, do not add the polyoxyethylene glycol (PEG#1000 of number-average molecular weight 1000, Japan Oil Co), and add 0.2mol isophorone diisocyanate to replace and add 0.3mol isophorone diisocyanate, in addition, to operate equally with Production Example 1, obtain dimethyl siloxane (methyl) origoester acrylate of number-average molecular weight about 2000.
< Production Example 14>
In Production Example 1, add 0.22mol isophorone diisocyanate to replace adding 0.3mol isophorone diisocyanate, in addition, to operate equally with Production Example 1, obtain dimethyl siloxane (methyl) origoester acrylate of number-average molecular weight about 40000.
< Production Example 15>
132.6g isobornyl acrylate, 0.03g dibutyl tin laurate stirring is added in the silicone compounds [KCC of SHIN-ETSU HANTOTAI manufactures, X-22-176DX] obtained by polydimethylsiloxane terminal-modified one-tenth glycol in reaction vessel, at 30.0g.Then, 3.14g hexamethylene diisocyanate (HDI) [Evonik Degussa GmbH manufactures] is at room temperature added.Be heated 50 DEG C, make it react 3 hours at 100 rpm, obtain carbamate prepolymer solution.In the pre-polymer solution total amount obtained, add 2.24g vinylformic acid 2-hydroxyl ethyl ester, stir 6 hours further, reaction is terminated, obtains siloxane oligomer.
The preparation of < Photocurable resin composition and evaluation >
According to the formula shown in table 1 ~ 6, in whipping appts, drop into each composition and mix, preparing Photocurable resin composition.The Photocurable resin composition obtained is applied to the upper surface of the base material formed by FRP (manufacture of DICMAT (registered trademark) 2415, DIC Chemical Co., Ltd) with thickness 20 μm.Then, UV irradiation (1000mW/cm is carried out 2, 4000mJ/cm 2) Photocurable resin composition is solidified, obtain sample.By following method evaluation water-repellancy, slipperiness, obtain the result shown in table 1 ~ 6.Wherein, in table 1 ~ 6, initially refer to after just making sample, after long duration test, refer to that dipping is after 50 hours in the water of 50 DEG C.
(1) consistency
The evaluation of consistency is undertaken by visual.Judge consistency when adding (A) dimethyl siloxane (methyl) origoester acrylate as (B) optical polymerism oligopolymer of matrix resin and/or (C) photopolymerization monomer according to following benchmark.
Zero: transparent
△: thin gonorrhoea
×: dense gonorrhoea
(2) water-repellancy
The evaluation of water-repellancy is that the contact angle measuring water carries out.Wherein, the mensuration of contact angle uses the DM-500 that consonance interface science Co., Ltd. manufactures.Base material drips the water droplet of 1.5 μ L, measures the water contact angle after just having dripped and after long duration test.Carry out 3 times to measure, using the value of its mean value as contact angle.
(3) slipperiness
The evaluation of slipperiness is that the landing angle measuring water is carried out.Wherein, the evaluation of slipperiness uses DM-500 and DM-SA that consonance interface science Co., Ltd. manufactures.Base material drips the water droplet of 30 μ L, with the speed of 7.5 degree/second, Stage microscope is tilted, water droplet is started the value of angle as landing angle of movement.Carry out 2 times to measure, using the value of its mean value as landing angle.
[table 1]
[table 2]
[table 3]
[table 4]
[table 5]
[table 6]
(Miwon company manufactures dimethyl siloxane (methyl) origoester acrylate that * 1 makes (q=3) shown in (a) general formula (2) (the total carbon number 3 of the R in general formula (1)) polysiloxane polyhydric alcohol, (b) obtains as the isophorone diisocyanate (IPDI) of isocyanic ester and the reaction of (c) (methyl) acrylate monomer, " SIU1300 ", number-average molecular weight: about 7000, functional group number 6)
(Miwon company manufactures dimethyl siloxane (methyl) origoester acrylate that * 2 make (q=3) shown in (a) general formula (2) (the total carbon number 3 of the R in general formula (1)) polysiloxane polyhydric alcohol, (b) obtains as the isophorone diisocyanate (IPDI) of isocyanic ester and the reaction of (c) (methyl) acrylate monomer, " SIU1500 ", number-average molecular weight: about 8000, functional group number 10)
Dimethyl siloxane (methyl) origoester acrylate obtained in * 3 Production Examples 1
* dimethyl siloxane (methyl) origoester acrylate obtained in 3-2 Production Example 2
* dimethyl siloxane (methyl) origoester acrylate obtained in 3-3 Production Example 3
* dimethyl siloxane (methyl) origoester acrylate obtained in 3-4 Production Example 4
* dimethyl siloxane (methyl) origoester acrylate obtained in 3-5 Production Example 5
* dimethyl siloxane (methyl) origoester acrylate obtained in 3-6 Production Example 6
* dimethyl siloxane (methyl) origoester acrylate obtained in 3-7 Production Example 7
* dimethyl siloxane (methyl) origoester acrylate obtained in 3-8 Production Example 8
* dimethyl siloxane (methyl) origoester acrylate obtained in 3-9 Production Example 9
* dimethyl siloxane (methyl) origoester acrylate obtained in 3-10 Production Example 10
* dimethyl siloxane (methyl) origoester acrylate obtained in 3-11 Production Example 11
* dimethyl siloxane (methyl) origoester acrylate obtained in 3-12 Production Example 12
* dimethyl siloxane (methyl) origoester acrylate obtained in 3-13 Production Example 13
* dimethyl siloxane (methyl) origoester acrylate obtained in 3-14 Production Example 14
The siloxane oligomer obtained in * 4 Production Examples 15
* 5CHISSO CORPORATION manufactures, " FM-0711 ", the acrylic acid modified dimethyl silicone oil of single terminal methyl group, number-average molecular weight (Mn) 1000, the compound outside the right shown in following general formula (3)
Wherein, in general formula (3), R represents alkyl, and Me represents methyl, and n represents arbitrary integer.Herein, R is set to alkyl to eliminate the reactivity of end, does not have essential attributes to the present invention.
* 6CHISSO CORPORATION manufactures, " FM-7711 ", the acrylic acid modified dimethyl silicone oil of two terminal methyl group, number-average molecular weight (Mn) 1000, proportion 0.98, specific refractory power 1.419, viscosity 20mm 2/ s, the compound outside the right shown in following general formula (4)
Wherein, in general formula (4), Me represents methyl, and n represents arbitrary integer.
* 7 urethane acrylate oligomers with 1,2-polyoxybutylene unit synthesized by following method
* 7-2 Kyoeisha Chemical Co., Ltd. manufactures UF-8001
* 8 Kyoeisha Chemical Co., Ltd. manufacture, 1,6 hexanediol diacrylate, SP value=19.6 (J/cm 3) 0.5
* 9 Industrial Co., Ltd of Xin Zhong village manufacture, 2-acryloyloxyethyl succinate, SP value=22.7 (J/cm 3) 0.5
* 10Ciba Specialty Chemicals manufactures, " IRGACURE184 ", 1-hydroxy-cyciohexyl-benzophenone
< has the synthetic method > of the urethane acrylate oligomer of 1,2-polyoxybutylene unit
Take potassium hydroxide as catalyzer, at temperature of reaction 110 DEG C, make 1mol propylene glycol (Kanto Kagaku K. K.'s manufacture) and 12mol butylene oxide ring carry out addition, obtain polyvalent alcohol.In the reaction vessel that nitrogen ingress pipe, agitator and prolong are housed, in this polyvalent alcohol, drop into 2mol2,4-tolylene diisocyanate, at 70 DEG C, make it react 2 hours.Then the dibutyl tin laurate as catalyzer of 4mol vinylformic acid 2-hydroxyl ethyl ester, trace is added lentamente, at 70 DEG C, make it react 15 hours further, obtain the urethane acrylate oligomer containing 1,2-butyleneglycol unit of number-average molecular weight about 1500.
The value with the normal heptane accommodation degree of the urethane acrylate oligomer of 1,2-polyoxybutylene unit obtained thus is 1.0g/10g.
From the embodiment of table 1 ~ 6 and the result of comparative example, polysiloxane polyhydric alcohol shown in (a) aforementioned formula (1), (b) isocyanic ester and (c) end are had can carry out reacting with (methyl) acrylate monomer of the functional group of isocyanate reaction by using (A) and dimethyl siloxane (methyl) origoester acrylate that obtains, can obtain can in long-time the Photocurable resin composition of raising water-repellancy and slipperiness.

Claims (9)

1. a Photocurable resin composition, is characterized in that, contains:
(A) make the polysiloxane polyhydric alcohol shown in (a) following general formula (1), (b) isocyanic ester and (c) end have and can carry out reacting with (methyl) acrylate monomer of the functional group of isocyanate reaction and dimethyl siloxane (methyl) origoester acrylate obtained;
Can with the copolymerization of described (A) dimethyl siloxane (methyl) origoester acrylate, (B) optical polymerism oligopolymer and/or (C) photopolymerization monomer; And
(D) Photoepolymerizationinitiater initiater;
Described (B) optical polymerism oligopolymer for having (methyl) origoester acrylate of 1,2-polyoxybutylene unit,
Wherein, in described general formula (1), n represent with the number-average molecular weight of described (A) dimethyl siloxane (methyl) origoester acrylate be 700 ~ 40000 the optional integer of mode, R represents the alkylidene group of total carbon number 1 ~ 30 or has the functional group of total carbon number 1 ~ 30 of ehter bond.
2. Photocurable resin composition according to claim 1, it is characterized in that, the equivalence ratio (isocyanate group/hydroxyl) of the hydroxyl in the polysiloxane polyhydric alcohol shown in the isocyanate group in described (b) isocyanic ester and described (a) general formula (1) is greater than 100/100 and is less than 300/100.
3. Photocurable resin composition according to claim 1 and 2, is characterized in that, the solubility parameter (SP value) of described (C) photopolymerization monomer is 20.0 (J/cm 3) 1/2below.
4. Photocurable resin composition according to claim 1 and 2, is characterized in that, described (C) photopolymerization monomer comprises the compound shown in following general formula (A),
(CH 2=CR 1cOO) nr 2general formula (A)
Wherein, in described general formula (A), R 1represent hydrogen atom or methyl, R 2represent the alkyl of the n valency of carbon number 5 ~ 20, n represents the integer in the scope of 1 ~ 4.
5. Photocurable resin composition according to claim 1 and 2, is characterized in that, described (b) isocyanic ester is the polyisocyanate compound in molecular structure with cyclic skeleton.
6. Photocurable resin composition according to claim 1 and 2, is characterized in that, in described (c) (methyl) acrylate monomer can be hydroxyl with the functional group of isocyanic ester radical reaction.
7. Photocurable resin composition according to claim 1 and 2, it is characterized in that, relative to the total of described (B) optical polymerism oligopolymer and/or (C) photopolymerization monomer, the content of described (A) dimethyl siloxane (methyl) origoester acrylate is 0.05 quality % ~ 10 quality %.
8. a Zhong Shi district component, is characterized in that having:
By the coating layer of the Photocurable resin composition solidification according to any one of claim 1 ~ 7; And substrate layer.
9. a functional panel, is characterized in that, has:
By the coating layer of the Photocurable resin composition solidification according to any one of claim 1 ~ 7; And substrate layer.
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JP5307511B2 (en) * 2008-11-07 2013-10-02 ディーエイチ・マテリアル株式会社 Radical polymerizable resin composition for film formation
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