CN103687882A - 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
CN103687882A
CN103687882A CN201280035678.2A CN201280035678A CN103687882A CN 103687882 A CN103687882 A CN 103687882A CN 201280035678 A CN201280035678 A CN 201280035678A CN 103687882 A CN103687882 A CN 103687882A
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methyl
acrylate
resin composition
photocurable resin
aforementioned
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CN103687882B (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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)

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 Qi Shi district member and functional panel
Technical field
The present invention relates to Photocurable resin composition and use Qi Shi district member and functional panel, relating in particular to and can in long-time, improve the Photocurable resin composition of water-repellancy and slipperiness (can easily remove the water skiing of surperficial water droplet) and use Qi Shi district member and functional panel.
Background technology
As the functional panel (panel) of material of construction, it is the metope of metope, ground or top ceiling as buildings and the member that configures has been endowed the various functions such as soundproof effect, moisture control performance according to the place of its configuration.Such functional panel especially when as the bathroom of premises, toilet or Deng Shi district, kitchen member, need to have the various characteristicses such as water-repellancy, slipperiness that can tolerate harsher environment for use.
To this, attempted the composition that has reduced surface free energy by the little low surface free energy compound of compounding surface free energy to coat component surface, to member, give good water-repellancy, make dirt be difficult for adhering to, as above-mentioned low surface free energy compound, use the hydrophobic materials such as fluoro-resin, siloxane-based compound.
For example, in following patent documentation 1, disclose surface and there is the paint solidification Wu Shi district member that contains low surface free energy compound, and then, as low surface free energy compound, silicone resin compound, fluoro-resin compound are disclosed.
In addition, in following patent documentation 2, disclose on substrate resin surface and formed low surface free energy layer and make 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 that 90 degree are above and below 170 degree, and the landing angle of the surface of this resin molded body and water is that 1 degree is above and below 80 degree.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2002-69378 communique
Patent documentation 2: TOHKEMY 2000-233156 communique
Summary of the invention
the problem that invention will solve
Yet, state before use in the middle of the low surface free energy surface of low surface free energy compound making, although use surface that fluoro-resin compound is made to repel water on this surface the glomerate water droplet of shape, often this water droplet of discovery strongly adheres to from the teeth outwards and not and drops.On the other hand, even if use initial landing angle, the surface of silicone resin compound making little, along with reusing, also exist smoothness of the surface reduction, landing angle to become large tendency.Therefore, also attempted, by making surface roughening etc. that surperficial contact angle is increased as much as possible, the water droplet adhering to being dropped from surface, but the surface of having carried out like this roughening etc. aspect weather resistance, at dirt, easily adhere to aspect existing problems.
And then conventionally also there is the problem poor with the consistency of matrix resin in low surface free energy compound as above.
Therefore, the object of the invention is to, in order to address the above problem, to provide and can in long-time, improve the Photocurable resin composition of water-repellancy and slipperiness.In addition, another object of the present invention be to provide have by above-mentioned Photocurable resin composition solidify the coating layer form, water-repellancy and slipperiness maintain good Shi district's member and functional panel in long-time.
for the scheme of dealing with problems
The inventor etc. conduct in-depth research in order to reach above-mentioned purpose, found that, by the constituent as Photocurable resin composition, use (A) to make (a) polysiloxane polyhydric alcohol (silicone polyol), (b) isocyanic ester, (c) end has dimethyl siloxane (methyl) origoester acrylate that can react with (methyl) acrylate monomer of the functional group of isocyanate reaction and obtain, good with the consistency of matrix resin, can form the sliding aqueous surface that can easily remove surperficial water droplet, and can form the overlay film with the weather resistance of can withstand prolonged using, thereby completed 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 inventor, by being made as, the equivalence ratio (NCO/-OH) of the hydroxyl (OH) in the isocyanate group (NCO) in (b) isocyanic ester and (a) polysiloxane polyhydric alcohol is greater than 100/100 and be below 300/100, can make the prepolymer that end has isocyanate group, then, the isocyanate group of prepolymer end is reacted with the monomer for example with hydroxyl and (methyl) acryl, can make high dimethyl siloxane (methyl) origoester acrylate (dimethyl silicone(meth) the acrylate oligomer of water-repellancy that end has (methyl) acryl), thereby completed the present invention.
That is, Photocurable resin composition of the present invention is characterised in that, contains:
(A) make the polysiloxane polyhydric alcohol shown in (a) following general formula (1), (b) isocyanic ester and (c) end there is dimethyl siloxane (methyl) origoester acrylate that can react with (methyl) acrylate monomer of the functional group of isocyanate reaction and obtain; 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.
Figure BDA0000458512700000031
Wherein, in aforementioned formula (1), n represents to take the optional integer of mode that the number-average molecular weight of aforementioned (A) dimethyl siloxane (methyl) origoester acrylate is 700～40000, and 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 isocyanate group in aforementioned (b) isocyanic ester and the equivalence ratio (isocyanate group/hydroxyl) of the hydroxyl in the polysiloxane polyhydric alcohol shown in aforementioned (a) general formula (1) are greater than 100/100 and be below 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, for a kind of separately, also can combine two or more.Here, the SP value while using two or more photopolymerization monomer refers to, the SP value that each monomer is had is multiplied by each compounding ratio (mass ratio) (monomer total amount being made as to the ratio of each monomer of 1 o'clock), the value that these products summations are obtained.For example, with respect to photopolymerization monomer total amount 1, during the photopolymerization monomer of the photopolymerization monomer of the amount compounding SP value 19.0 with 3/4, the amount compounding SP value 21.0 with 1/4, according to following formula (X), obtain the SP value of used photopolymerization monomer integral body.
The SP value of photopolymerization monomer=(19.0 * 3/4)+(21.0 * 1/4)=19.5 (X)
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 2the alkyl that represents the n valency of carbon number 5～20, n represents the integer in 1～4 scope.
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 in molecular structure, to have the polyisocyanate compound of 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, with respect to (B) optical polymerism oligopolymer and/or (C) total of photopolymerization monomer, the content of aforementioned (A) dimethyl siloxane (methyl) origoester acrylate is 0.05 quality %～10 quality %.
In addition, wet district of the present invention member is characterised in that to have: Photocurable resin composition is solidified to the coating layer forming; And substrate layer.
In addition, functional panel of the present invention is characterised in that to have: Photocurable resin composition of the present invention is solidified to the coating layer forming; And substrate layer.
the effect of invention
According to the present invention, a kind of Photocurable resin composition can be provided, and it comprises: (A) make the polysiloxane polyhydric alcohol shown in (a) general formula (1), (b) isocyanic ester and (c) end there is dimethyl siloxane (methyl) origoester acrylate that can react with (methyl) acrylate monomer of the functional group of isocyanate reaction and obtain; (B) optical polymerism oligopolymer and/or (C) photopolymerization monomer; And (D) Photoepolymerizationinitiater initiater, described Photocurable resin composition can be in long-time raising water-repellancy and slipperiness.In addition, can provide have by described Photocurable resin composition solidify the coating layer form, water-repellancy and slipperiness well Shi district's member 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, contain (E) other composition as required.
In Photocurable resin composition of the present invention, (A) dimethyl siloxane (methyl) origoester acrylate is because the surface at the dimethyl siloxane position of (a) polysiloxane polyhydric alcohol using as one of starting raw material can be low, therefore can play a role as low surface free energy compound, for example, can improve and there is coating layer Shi district's member of being obtained by this Photocurable resin composition and water-repellancy and the slipperiness of functional panel.
In addition, in Photocurable resin composition of the present invention, (A) segregation is from the teeth outwards in long-time for dimethyl siloxane (methyl) origoester acrylate, as its result, for example, can be in long-time raising there is coating layer Shi district's member of being obtained by this Photocurable resin composition and water-repellancy and the slipperiness of functional panel.
< (A) dimethyl siloxane (methyl) origoester acrylate >
(A) dimethyl siloxane (methyl) origoester acrylate using in Photocurable resin composition of the present invention make (a) polysiloxane polyhydric alcohol composition, (b) isocyanate prepolymer composition and (c) (methyl) acrylate monomer composition react and obtain.Should for example can obtain as follows by (A) dimethyl siloxane (methyl) origoester acrylate: (a) polysiloxane polyhydric alcohol is reacted with (b) isocyanic ester, part or all of synthetic 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.
By obtain dimethyl siloxane (methyl) origoester acrylate with isocyanic ester, can synthesize the prepolymer with any repeat number, the physics value of the oligopolymer that can adjust molecular weight thus or obtain (flexibility, intensity, cementability etc.), and can make molecule contain the high amino-formate bond of polarity of any number, therefore, there is the Compatibility Design easily carrying out with matrix resin.
Number-average molecular weight as aforementioned (A) dimethyl siloxane (methyl) origoester acrylate, is not particularly limited, and can suitably select according to object, is preferably 1000～40000.Aforementioned number-average molecular weight can, with GPC by polystyrene standard production standard curve, be obtained by the retention time of sample.The mobile phase solvent of GPC can be used tetrahydrofuran (THF), chloroform.In addition, detector can use refractometer (RI), UV detector etc.Make to obtain in this way number-average molecular weight less than 1000 time, (A) relative quantity at the dimethyl siloxane position in dimethyl siloxane (methyl) origoester acrylate reduces, and therefore in order to bring into play sufficient effect, need to increase addition.On the other hand, number-average molecular weight was over 40000 o'clock, with can with (B) optical polymerism oligopolymer of (A) dimethyl siloxane (methyl) origoester acrylate polymerization and/or (C) consistency of photopolymerization monomer obviously reduce and occur separated, and because cross-linking density reduces, therefore film surface becomes soft, forms the surface easily scratching.
(A) dimethyl siloxane (methyl) origoester acrylate except contain the polysiloxane polyhydric alcohol shown in (a) general formula (1), (b) isocyanic ester, (c) end have can with (methyl) acrylate monomer of the functional group of isocyanate reaction, can also contain (d) other polyhydroxy reactant.Now, by (a) polysiloxane polyhydric alcohol, (d) other polyvalent alcohol and (b) isocyanic ester copolymerization, part or all of synthetic 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, thereby obtain.
By containing (d) other polyhydroxy reactant, can at random adjust water-repellancy, with the consistency of matrix resin, the hardness of cured article etc.
Content as aforementioned (A) dimethyl siloxane (methyl) origoester acrylate, be not particularly limited, can suitably select according to object, with respect to (B) optical polymerism oligopolymer and/or (C) total of photopolymerization monomer, be preferably 0.05 quality %～10 quality %, 0.1 quality %～5.0 quality % more preferably.Herein, (A) content of dimethyl siloxane (methyl) origoester acrylate is the amount (amount of solids component) of the effective constituent of (A) dimethyl siloxane (methyl) origoester acrylate.
Aforementioned when the quantity not sufficient 0.05 quality %, sometimes cannot improve fully water-repellancy, the water skiing of the article that are coated with Photocurable resin composition of the present invention, while surpassing 10 quality %, with (B) optical polymerism oligopolymer and/or (C) the consistency deterioration of photopolymerization monomer, sometimes can not get uniform cured article.On the other hand, the content of aforementioned (A) dimethyl siloxane (methyl) origoester acrylate is in aforementioned preferred scope time, (A) surface segregation of dimethyl siloxane (methyl) origoester acrylate becomes more obvious, and the article that are 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, it is also favourable from the viewpoint of cost that the content of (A) dimethyl siloxane (methyl) origoester acrylate is located in aforementioned preferred scope.
-(a) polysiloxane polyhydric alcohol-
(a) polysiloxane polyhydric alcohol using as one of starting raw material of aforementioned (A) dimethyl siloxane (methyl) origoester acrylate is represented by following general formula (1).
Figure BDA0000458512700000081
Wherein, in aforementioned formula (1), as long as n represent be take the optional integer of the mode that the number-average molecular weight of aforementioned (A) dimethyl siloxane (methyl) origoester acrylate is 700～40000 (mode that the number-average molecular weight of aforementioned polysiloxane polyhydric alcohol of take is 500～40000), just be not particularly limited, can suitably select according to object.
In addition, in aforementioned formula (1), as R, as long as for the alkylidene group of total carbon number 1～30 or there is the functional group of total carbon number 1～30 of ehter bond, be just not particularly limited, can suitably select according to object.
Alkylidene group as aforementioned total carbon number 1～30, be not particularly limited, can suitably select according to object, such as listing 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, can suitably select according to object, for example, can list-C 3h 6-O-C 2h 4-,-C 3h 6-(OC 2h 4) m-: m makes total carbon number be no more than 30 integer ,-C 2h 4-O-C 2h 4-,-C 3h 6-O-C 3h 6-etc.
It is the viewpoint for dimethyl siloxane (dimethyl silicone) concentration, thermotolerance etc. that total carbon number of R is made as below 30.As R, from the viewpoint of easily obtaining in market, preferably propylidene or-C 3h 6-O-C 2h 4-.
And then an example as aforementioned formula (1), can list following general formula (2).
Figure BDA0000458512700000082
Wherein, in aforementioned formula (2), n represents to take the optional integer of the mode that the number-average molecular weight of aforementioned (A) dimethyl siloxane (methyl) origoester acrylate is 700～40000 (mode that the number-average molecular weight of aforementioned polysiloxane polyhydric alcohol of take is 500～40000), p represents the integer in 0～9 scope, and q represents the integer in 3～9 scope.
Commercially available product as aforementioned (a) polysiloxane polyhydric alcohol, be not particularly limited, can suitably select according to object, (Gelest company manufactures: number-average molecular weight ≈ 700:p=0 for example can to list 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 use separately a kind of, also can be used in combination two or more.
In aforementioned formula (2), p and q represent the integer in above-mentioned scope.By changing their length, can change the consistency with matrix resin, on the other hand, when long, the siloxane concentrations in structure relatively reduces, and therefore cannot bring into play sufficient function.P and q are in above-mentioned scope time, on improving in long-time as the water-repellancy of target of the present invention and the object of slipperiness (can easily remove the water skiing of surperficial water droplet), do not affect, and can show fully function.
In addition, aforementioned (a) polysiloxane polyhydric alcohol for example can be manufactured by utilizing platinum group catalyst to make to carry out addition reaction containing the dimethyl polysiloxane of end Si-H base and compound that each end has hydroxyl and alkenyl.
Figure BDA0000458512700000091
Number-average molecular weight (Mn) as aforementioned (a) polysiloxane polyhydric alcohol, as long as be 500～20000, is just not particularly limited, and can suitably select according to object.Aforementioned number-average molecular weight can, with GPC by polystyrene standard production standard curve, be obtained by the retention time of sample.The mobile phase solvent of GPC can be used tetrahydrofuran (THF), chloroform.In addition, detector can use refractometer (RI), UV detector etc.
During aforementioned number-average molecular weight less than 500, the relative quantity at the dimethyl siloxane position in structure reduces, therefore in order to bring into play sufficient effect, need to increase addition, over 20000 o'clock, with can with (B) optical polymerism oligopolymer of (A) dimethyl siloxane (methyl) origoester acrylate polymerization and/or (C) consistency of photopolymerization monomer obviously reduce and occur separated, and because cross-linking density reduces, therefore film surface becomes soft, forms the surface easily scratching.
-(b) isocyanic ester-
(b) isocyanic ester as one of starting raw material as aforementioned (A) dimethyl siloxane (methyl) origoester acrylate, be not particularly limited, can suitably select according to object, in preferred molecular structure, there is the polyisocyanate compound of cyclic skeleton.
Aforementioned (b) isocyanic ester is while having the polyisocyanate compound of cyclic skeleton in molecular structure, and (A) dimethyl siloxane (methyl) origoester acrylate self being obtained by isocyanic ester also has cyclic skeleton in molecular structure.The cyclic skeleton being present in the molecular structure of this (A) dimethyl siloxane (methyl) origoester acrylate forms steric hindrance, suppress the inside that (A) dimethyl siloxane (methyl) origoester acrylate enters Photocurable resin composition, make the long-time segregation of (A) dimethyl siloxane (methyl) origoester acrylate from the teeth outwards.
The polyisocyanate compound in molecular structure as aforementioned (b) isocyanic ester with cyclic skeleton, as long as there is cyclic skeleton (ring texture part) and there are a plurality of isocyanate group (NCO yl) in molecular structure, just be not particularly limited, can suitably select according to object, for example can list naphthalene diisocyanate (NDI), tolylene diisocyanate (TDI), Xylene Diisocyanate (XDI), isophorone diisocyanate (IPDI), diphenylmethanediisocyanate (MDI), PPDI (PPDI), tolidine vulcabond (TODI), dianisidine vulcabond (DADI), dicyclohexyl methane diisocyanate (H12MDI), 1, two (isocyanato-methyl) hexanaphthenes (H6XDI) of 3-, tetramethylxylene diisocyanate (TMXDI), norbornylene vulcabond (NBDI), and the NCO terminal amino group manthanoate prepolymer that comprises these structures etc.These can use separately a kind of, also can be used in combination two or more.
Wherein, preferred naphthalene diisocyanate (NDI), tolylene diisocyanate (TDI), Xylene Diisocyanate (XDI), isophorone diisocyanate (IPDI).
Aforementioned (a) polysiloxane polyhydric alcohol and (b) consumption of isocyanic ester can suitably change, and (b) equivalence ratio (NCO/-OH) of the hydroxyl in the isocyanate group in isocyanic ester (NCO) and (a) polysiloxane polyhydric alcohol is preferably more than 100/100 and be the scope below 300/100.
In addition, during synthetic aforementioned (A) dimethyl siloxane (methyl) origoester acrylate, (b) isocyanic ester is reacted with the hydroxyl in (a) polysiloxane polyhydric alcohol, when part or all of synthetic end has the carbamate prepolymer of isocyanate group, make the equivalence ratio (NCO/-OH) of the hydroxyl in isocyanate group (NCO) in (b) isocyanic ester and (a) polysiloxane polyhydric alcohol be greater than 1.
By making like this equivalence ratio (NCO/-OH) of the hydroxyl in isocyanate group (NCO) in (b) isocyanic ester and (a) polysiloxane polyhydric alcohol be greater than 1, can synthesize the prepolymer that two ends are isocyanate group, utilize this isocyanate group, can with (c) (methyl) acrylate monomer in functional group's (for example, isocyanate group) react.
In the reacting of aforementioned (a) polysiloxane polyhydric alcohol and (b) isocyanic ester, preferably use the catalyzer of urethane reaction use.
As the anti-applications catalyst of aforementioned urethane, be not particularly limited, can suitably select according to object, such as listing the organo-tin compounds such as dibutyl tin laurate, dibutyltin diacetate, thiocarboxylic acid dibutyl tin, two toxilic acid dibutyl tins, 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 use separately a kind of, also can be used in combination two or more.
Wherein, preferably have machine tin compound.
Consumption as the anti-applications catalyst of aforementioned urethane, is not particularly limited, and can suitably select according to object, with respect to 100 mass parts aforementioned (a) polysiloxane polyhydric alcohol, is preferably 0.001 mass parts～2.0 mass parts.
-(c) (methyl) acrylate monomer-
(c) (methyl) acrylate monomer as one of starting raw material 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, can suitably select according to object.
As aforementioned can with the functional group of isocyanate reaction, be not particularly limited, can suitably select according to object, such as listing hydroxyl (OH), carboxyl (COOH), primary amino, secondary amino group etc.
Wherein, from the abundant species of the reactive quality with aforementioned isocyanic ester, commercially available product and the aspect easily obtaining, be preferably hydroxyl.
As aforementioned (methyl) acrylate monomer with hydroxyl (OH), be not particularly limited, can suitably select according to object, such as listing (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 group propyl ester, (methyl) vinylformic acid 4-hydroxyl cyclohexyl, 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, can suitably select according to object, such as listing succsinic acid 2-(methyl) acryloxy ethyl ester, succsinic acid 2-acryloxy ethyl ester, phthalic acid monohydroxy ethyl (methyl) acrylate etc.
As aforementioned (methyl) acrylate monomer with amino, be not particularly limited, can suitably select according to object, such as listing (methyl) acrylate that side chain is 1-amino-ethyl, (methyl) acrylate that side chain is 1-aminopropyl etc.
(c) (methyl) acrylate monomer also can structure contain can with the functional group of isocyanate reaction and (methyl) acryl of optical polymerism.The quantity that can use aforementioned (methyl) acryl is (c) (methyl) acrylate monomer for arbitrarily, quantity more (more multifunctional), and (A) dimethyl siloxane (methyl) origoester acrylate is more multifunctional.Conventionally, functional group's number is more, and the reactivity of (methyl) acrylate monomer and (B) optical polymerism oligopolymer or (C) photopolymerization monomer is higher, but functional group's number is when too much, and due to steric hindrance, reactivity reduces sometimes.Consider these aspects, functional group's number of (methyl) acrylate monomer is preferably between 2～10, more preferably functional group's number many (approaching 10) in this scope.In this scope, functional group's number is more, and being cross-linked of (methyl) acrylate monomer is denser, therefore 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 separately a kind of, also can be used in combination two or more.
The consumption of above-mentioned (c) (methyl) acrylate monomer can suitably change, make with respect to by (a) polysiloxane polyhydric alcohol and (b) isocyanic ester in molecular structure, have isocyanate group (NCO) in the reaction product (carbamate prepolymer) that the polyisocyanate compound of cyclic skeleton forms, in (c) (methyl) acrylate monomer can with the equivalent (functional group/-NCO) of the functional group of isocyanate reaction more than 1 equivalent use.
< (B) optical polymerism oligopolymer and/or (C) photopolymerization monomer >
(B) the optical polymerism oligopolymer using in Photocurable resin composition of the present invention and/or (C) photopolymerization monomer contain free-radical polymerised reactive group, for example (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) the compounding amount of optical polymerism oligopolymer and (C) photopolymerization monomer by quality ratio for 100:0～0:100, be preferably 80:20～20:80, the scope of 30:70～70:30 more preferably.(C) when the compounding amount of photopolymerization monomer is very few, the viscosity rise of the resin Photocurable composition obtaining, the coating while worrying coating worsens, and possibly cannot guarantee fully the physical property such as chemical proofing and resistance to dyeability.In addition, when the compounding amount of photopolymerization monomer is too much, there is the flexibility reduction of making while filming and the tendency that fragility uprises.
-(B) optical polymerism oligopolymer-
As aforementioned (B) optical polymerism oligopolymer, be not particularly limited, can suitably select according to object, preferably there is an above 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 is because polarity is low, therefore good with the consistency of (A) dimethyl siloxane (methyl) origoester acrylate, can in wide region, add (A) dimethyl siloxane (methyl) origoester acrylate.Therefore, even when the addition of (A) dimethyl siloxane (methyl) origoester acrylate is many, also can suppress gonorrhoea, layering etc., can make the characteristic after solidifying even, and the outward appearance of filming is good, use Qi Shi district member and functional panel also can form good physical property and outward appearance.In addition, Photocurable resin composition is solidified and the hydrophobicity of the resin that obtains is high, therefore strong to the tolerance of the staining agents such as the clean-out system using in Shui Heshi district, hair dye, dirt is difficult for adhering to, and the permanent stability of water skiing become better.
In addition, about aforementioned (methyl) origoester acrylate (A), be low polarity, particularly, can represent by the value of normal heptane degree of holding (tolerance), more than above-mentioned value is preferably 0.5g/10g, more preferably more than 0.7g/10g.It should be noted that, normal heptane degree of holding refers to, on one side 10g resin is remained on to 25 ℃, drip wherein normal heptane on one side, until the value of the amount of the normal heptane that gonorrhoea can be added (g) 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, can suitably select according to object, such as listing carbamate system (methyl) origoester acrylate, epoxy system (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 by polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene ether diol, bisphenol A type epoxy resin, phenol novolak type epoxy resin, polyvalent alcohol and 6-caprolactone affixture etc. synthesize with (methyl) acrylic acid reaction, or synthesize by (methyl) acrylic compound urethane that makes polyisocyanate compound and there is hydroxyl.
Aforementioned (B) optical polymerism oligopolymer can be any number of in simple function oligopolymer, 2 functional oligomers, multifunctional oligopolymer, from realizing the viewpoint of the appropriate cross-linking density of the Photocurable resin composition obtaining, is preferably multifunctional oligopolymer.
In the middle of aforementioned (B) optical polymerism oligopolymer, from giving the viewpoint as the suitable characteristic of district's member and functional panel that wets, preferably the carbamate of chemical proofing excellence is (methyl) origoester acrylate.
Aforementioned carbamate system (methyl) origoester acrylate for example can be manufactured as follows: by (i) polyvalent alcohol and (ii) polyisocyanates synthesis of carbamates prepolymer, this carbamate prepolymer addition (iii) is had can be with the compound of the functional group of isocyanate reaction, for example have (methyl) acrylate of hydroxyl, thereby manufactures.
--(i) polyvalent alcohol--
The synthetic middle polyvalent alcohol using as aforementioned carbamate prepolymer, so long as there is the compound of a plurality of hydroxyls (OH), just be not particularly limited, can suitably select according to object, such as listing polyether glycol, polyester polyol, polytetramethylene glycol, polybutadiene polyol, oxirane modified polybutadiene polyvalent alcohol, polyisoprene polyvalent alcohol etc.These can use separately a kind of, also can be used in combination two or more.
Aforementioned polyether glycol can obtain by addition polymerization, such as can be by the oxiranes such as polyvalent alcohol addition of ethylene oxide, propylene oxide such as ethylene glycol, propylene glycol, glycerine, TriMethylolPropane(TMP), tetramethylolmethane, Sorbitol Powder be obtained, in addition, also can obtain polyether glycol by ring-opening polymerization.As aforementioned polyether glycol, be not particularly limited, can suitably select according to object polytetramethylene glycol (poly tetramethylene glycol) obtaining such as the ring-opening polymerization that can list by tetrahydrofuran (THF) (THF) etc.
Aforementioned polyester polyol can obtain by addition polymerization, for example can be 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 can obtain polyester polyol by ring-opening polymerization.As aforementioned polyester polyol, be not particularly limited, can suitably select according to object, the lactone obtaining such as the ring-opening polymerization that can list by 6-caprolactone is polyester polyol etc.
By using butylene oxide ring modified polyalcohol as aforementioned (i) polyvalent alcohol, can manufacture aforementioned (methyl) origoester acrylate with 1,2-polyoxybutylene unit.This butylene oxide ring modified polyalcohol be under the existence of alkaline catalysts, make polyvalent alcohol and 1,2 ?butylene oxide ring (BO) carry out addition polymerization and the polyether glycol that obtains.In addition, can be also 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 being obtained by GPC of these butylene oxide ring modified polyalcohols is generally 100～15000, is preferably 500～5000.
--(ii) polyisocyanates--
As aforementioned polyisocyanates, so long as there is the compound of a plurality of isocyanate group (NCO), just be not particularly limited, can suitably select according to object, such as listing 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 use separately a kind of, also can be used in combination two or more.
--the anti-applications catalyst of urethane--
In aforementioned carbamate prepolymer synthetic, preferably use the catalyzer of urethane reaction use.As the anti-applications catalyst of aforementioned urethane, be not particularly limited, can suitably select according to object, such as listing the organo-tin compounds such as dibutyl tin laurate, dibutyltin diacetate, thiocarboxylic acid dibutyl tin, two toxilic acid dibutyl tins, 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 use separately a kind of, also can be used in combination two or more.
Wherein, preferably have machine tin compound.
Consumption as the anti-applications catalyst of aforementioned urethane, is not particularly limited, and can suitably select according to object, with respect to 100 mass parts aforementioned (i) polyvalent alcohol, is 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 to have one can for example, with functional group's (, hydroxyl) of isocyanate reaction and have ((methyl) acryloxy [CH of functional group that shows above optical polymerism above with the compound of the functional group of isocyanate reaction 2=CHCOO-or CH 2=C (CH 3) COO-]) compound.
Aforementioned (iii) have can with the compound of the functional group of isocyanate reaction can with aforementioned carbamate prepolymer in isocyanate group addition.
As aforementioned (iii) have can with the compound of the functional group of isocyanate reaction, be not particularly limited, can suitably select according to object, for example can list (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, tetramethylolmethane three (methyl) acrylate, 2-hydroxyethyl vinyl ether, Diethylene Glycol mono vinyl ether, 4-hydroxy butyl vinyl ether, 3-ethyl-3-methylol trimethylene oxide, succsinic acid 2-(methyl) acryloxy ethyl ester, phthalic acid list hydroxyethyl (methyl) acrylate, side chain is 1-amino-ethyl (methyl) acrylate, side chain is 1-aminopropyl (methyl) acrylate etc.These can use separately a kind of, also can be used in combination two or more.
By compounding this (B) optical polymerism oligopolymer, the second-order transition temperature that coating layer Photocurable resin composition is curing and that obtain shows can be optimized, the Photocurable resin composition of the effect that can bring into play water-repellancy and slipperiness excellence can be accessed.
-(C) photopolymerization monomer-
As aforementioned (C) photopolymerization monomer, be not particularly limited, can suitably select according to object, preferably there is above (methyl) acryloxy [CH 2=CHCOO-or CH 2=C (CH 3) COO-] and (methyl) acrylate monomer, can be (i) simple function monomer, (ii) 2 functional monomers and (iii) any number of in multi-functional monomer.
It should be noted that, aforementioned (C) photopolymerization monomer can, for a kind of separately, can be also that combination is two or more.Here, the SP value while using two or more photopolymerization monomer refers to, the SP value that each monomer is had is multiplied by each compounding molar ratio (mass ratio) (monomer total amount being made as to the ratio of each monomer of 1 o'clock), the value that these products summations are obtained.For example, with respect to photopolymerization monomer total amount 1, during the photopolymerization monomer of the photopolymerization monomer of the amount compounding SP value 19.0 with 3/4, the amount compounding SP value 21.0 with 1/4, according to following formula (X), obtain the SP value of used photopolymerization monomer integral body.
The SP value of photopolymerization monomer=(19.0 * 3/4)+(21.0 * 1/4)=19.5 (X)
-(i) simple function monomer-
As aforementioned (i) simple function monomer, be not particularly limited, can suitably select according to object, for example can list (methyl) isobornyl acrylate, (methyl) vinylformic acid norbornene ester, (methyl) vinylformic acid three ring decyl ester, (methyl) vinylformic acid two cyclopentyl esters, (methyl) vinylformic acid dicyclopentenyl ester, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid benzyl ester, (methyl) vinylformic acid 4-butyl cyclohexyl, (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) vinylformic acid pentyl ester, (methyl) vinylformic acid isopentyl ester, (methyl) Ethyl acrylate, (methyl) vinylformic acid heptyl ester, (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) vinylformic acid Lauryl Ester, (methyl) stearyl acrylate base ester, (methyl) vinylformic acid myristyl ester, (methyl) vinylformic acid palmityl ester, (methyl) vinylformic acid iso stearyl ester, (methyl) vinylformic acid tetrahydro furfuryl ester, (methyl) vinylformic acid butoxyethyl, oxyethyl group Diethylene Glycol (methyl) acrylate, polyoxyethylene nonylplenyl ether acrylate, (methyl) vinylformic acid phenoxy ethyl, polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate, methoxyl group ethylene glycol (methyl) acrylate, (methyl) vinylformic acid ethoxy ethyl ester, methoxy poly (ethylene glycol) (methyl) acrylate, methoxyl group polypropylene glycol (methyl) acrylate, (methyl) vinylformic acid dimethylamino ethyl ester, (methyl) vinylformic acid diethylamino ethyl ester, (methyl) vinylformic acid 7-amino-3,7-dimethyl monooctyl ester etc.These can use separately a kind of, also can be used in combination two or more.
-(ii) 2 functional monomers-
As aforementioned (ii) 2 functional monomers, be not particularly limited, can suitably select according to object, for example can list 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, tristane 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, epoxy (methyl) acrylate that the diglycidylether that makes dihydroxyphenyl propane obtains with (methyl) acrylate addition etc.These can use separately a kind of, also can be used in combination two or more.
-(iii) multi-functional monomer-
As aforementioned (iii) multi-functional monomer, be not particularly limited, can suitably select according to object, such as listing 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 use separately a kind of, also can be used in combination two or more.
Solubility parameter (SP value) as aforementioned photopolymerization monomer, is not particularly limited, and can suitably select according to object, is preferably 20.0 (J/cm 3) 0.519.6 (J/cm more preferably below, 3) 0.5below.In addition, the lower value as aforementioned SP value, is not particularly limited, and is conventionally preferably 17.0 (J/cm 3) 0.5above.By making SP value low, improve with the consistency of (A) dimethyl siloxane (methyl) origoester acrylate, can in wide region, add (A) dimethyl siloxane (methyl) origoester acrylate.Therefore, even when the addition of (A) dimethyl siloxane (methyl) origoester acrylate is many, also can suppress gonorrhoea, layering etc., the outward appearance after solidifying is good, uses Qi Shi district member and functional panel also can form good outward appearance.
Herein, SP value (δ) conventionally by molar energy of vaporization (Δ Ev) and the molecular volume (V) of liquid, utilize following formula to define.
SP value (δ)=(Δ Ev/V) 0.5
And then SP value can only be calculated (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 of calculating 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,, containing heteroatoms, can not be that chain can be also ring-type.In addition, in group-CH 2-also can replace by use-CH=CH-.N is 1～4 integer.
That is, in general formula (A), for example, be chain and when the saturated monomer, R during n=1 2for the alkyl of carbon number 5～20, R during n=2 2alkylidene group for carbon number 5～20.And then, for chain and while being saturated monomer, R during n=3 2for alkane three bases (alkantriyl group) of carbon number 5～20, R during n=4 2alkane four bases (alkanetetrayl group) for carbon number 5～20.As this R 2, for example, have-CH 2cH 3,-CH 2cH 2cH 3,-CH (CH 3) CH 3, the alkyl such as cyclohexyl, suberyl, ring octyl group, ring nonyl, 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 bases, as C (CH 2-) 4shown in such alkane four bases etc.
R 2carbon number less than 5 time, in the situation that the alkyl of chain, the tendency that exists the SP value of monomer to rise, reduces with the consistency of (A) dimethyl siloxane (methyl) origoester acrylate, in the situation that the alkyl of ring-type self is difficult to obtain.In addition, R 2carbon number surpass at 20 o'clock, the tendency that exists the cross-linking density of the Photocurable resin composition obtaining to reduce.If cross-linking density exceeds necessarily, reduce, the staining agent such as hair dye is easily invaded coating layer inside, the worry that therefore exists plate to be colored.
Object lesson as the monomer shown in general formula (A), for example can list (methyl) isobornyl acrylate, 1, 6-hexylene glycol two (methyl) acrylate, dihydroxymethyl tristane two (methyl) acrylate, (methyl) vinylformic acid isopentyl ester, (methyl) vinylformic acid Lauryl Ester, (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, existence is owing to having SP value preferably and show the tendency of good low polarity, from can further improving the consistency with (A) dimethyl siloxane (methyl) origoester acrylate, 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) is because polarity is low, therefore good with the consistency of (A) dimethyl siloxane (methyl) origoester acrylate, can in wide region, add (A) dimethyl siloxane (methyl) origoester acrylate.Therefore, even when the addition of (A) dimethyl siloxane (methyl) origoester acrylate is many, also can suppress gonorrhoea, layering etc., the outward appearance after solidifying is good, uses Qi Shi district member and functional panel also can form good outward appearance.In addition, Photocurable resin composition is solidified and the hydrophobicity of the resin that obtains is high, therefore strong to the tolerance of the staining agents such as the clean-out system using in Shui Heshi district, hair dye, dirt is difficult for adhering to, and the permanent stability of water skiing become better.
In addition, functional group's number of aforementioned photopolymerization monomer is generally 1～6, is preferably 1～4.It should be noted that, functional group's number is 1 o'clock, the tendency that exists cross-linking density to reduce, but by using the monomer of cyclic skeleton, thereby second-order transition temperature uprises, and can keep good film physical property.In addition, functional group's number is 2～6, is preferably at 2～4 o'clock, therefore existence can moderately keep the tendency of the crosslinking reaction of Photocurable resin composition, can infer that easily more effectively suppressing staining agent particularly invades the phenomenon that the inner Er Shishi district's member of coating layer and functional panel are colored.Therefore, now also can effectively keep obtaining being formed with coating layer Shi district's member and the functional panel with suitable solidified nature under good didirtresistance and chemical proofing, resistance to chromatic prerequisite.
(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 using in Photocurable resin composition of the present invention has by light such as irradiation ultraviolet radiations and causes above-mentioned (A) dimethyl siloxane (methyl) origoester acrylate, (B) optical polymerism oligopolymer and/or (C) effect of the polymerization of photopolymerization monomer.
As aforementioned (D) Photoepolymerizationinitiater initiater, be not particularly limited, can suitably select according to object, for example can list 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid ester, 2,2-dimethoxy-2-phenyl methyl phenyl ketone, 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-dialkyl amido phenyl) ketone, the benzil derivatives such as benzil and benzil methyl ketal, the benzoin derivatives such as bitter almond oil camphor and bitter almond oil camphor ethyl isobutyl ether, benzoin iso-propylether, 2-hydroxy-2-methyl Propiophenone, 1-hydroxyl-cyclohexyl-benzophenone, xanthone, thioxanthone and thioxanthone derivates, fluorenes, TMDPO, two (2,6-dimethoxy benzoyls)-2,4,4-tri-methyl-amyl phosphine oxide, two (2,4,6-trimethylbenzoyl)-phenyl phosphine oxide, 2-methyl isophthalic acid-(4-methyl thio-phenyl)-2-morpholino propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone-1 etc.These can use separately a kind of, also can be used in combination two or more.
Compounding amount as aforementioned (D) Photoepolymerizationinitiater initiater in Photocurable resin composition of the present invention, be not particularly limited, can suitably select according to object, with respect to (A) dimethyl siloxane (methyl) origoester acrylate and (B) optical polymerism oligopolymer and/or (C) total 100 mass parts of photopolymerization monomer, be preferably the scope of 0.1 mass parts～10 mass parts.The compounding amount of aforementioned (D) Photoepolymerizationinitiater initiater is that 0.1 mass parts is when above, initiated polymerization fully, on the other hand, while surpassing 10 mass parts, the effect of initiated polymerization is saturated, on the other hand, painted becoming obviously, and also the cost of the raw material of Photocurable resin composition uprises.
Other composition of < (E) >
-photosensitizers-
In Photocurable resin composition of the present invention, consider required solidification reactivity, stability etc., can also further contain as required photosensitizers.This photosensitizers has by irradiating light and absorbs energy, and this energy or transfer transport are to polymerization starter and the effect of initiated polymerization.As this photosensitizers, can list ESCAROL 507 isopentyl ester etc.The compounding amount of these photosensitizerss, with respect to (A) optical polymerism siloxane oligomer and (B) optical polymerism oligopolymer and/or (C) total 100 mass parts of 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., can also contain as required stopper.As this stopper, can list quinhydrones, hydroquinone monomethyl ether, p methoxy phenol, 2,4-dimethyl-6-tert.-butyl phenol, 2,6-di-t-butyl-p-cresol, butyl hydroxyanisole, 3-hydroxythiophenol, alpha-nitroso-beta-naphthol, para benzoquinone, 2,5-dihydroxyl-para benzoquinone etc.The compounding amount of these stoppers, with respect to (A) dimethyl siloxane (methyl) origoester acrylate and (B) optical polymerism oligopolymer and/or (C) total 100 mass parts of 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, can list propylene glycol methyl ether acetate (PMA), methylethylketone (MEK), methyl iso-butyl ketone (MIBK) (MIBK), acetone, n-Butyl lactate etc.These diluting solvents can be used separately a kind of, also can be used in combination two or more.
Photocurable resin composition of the present invention can be used diluting solvent as described above as required, make coating aqueous, be applied to the surface on base material.Method as coating, be not particularly limited, can adopt known method, such as listing 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 member)
Aforementioned wet district member is characterised in that to have: Photocurable composition of the present invention is solidified to the coating layer forming; And substrate layer.Aforementioned wet district member is the member that needs surperficial water repellency.As aforementioned wet district member, be not particularly limited, can suitably select according to object, such as listing kitchen basin, materials for wall for kitchen use, wash stand, materials for wall, bathtub, ceiling material, bathroom floor panel material, table top, toilet, water tank etc. for bathroom for bathroom for bathroom.
(functional panel)
Functional panel of the present invention has curing coating layer and the substrate layer forming of Photocurable resin composition of the present invention, and for example, preferably this coating layer is formed on this substrate layer.
Thickness as functional panel integral body of the present invention, is not particularly limited, and can suitably select according to object, more than being conventionally preferably 2.5mm.In addition, the upper limit as the thickness of functional panel integral body of the present invention, is not particularly limited, and can suitably select according to object.Both are upper aforementioned coating layer can be formed on to front and back on substrate layer, also can be formed in as required the multilayered structure that is formed with the middle layer being formed by various materials on the basis of these substrate layers and coating layer between these layers.Therefore now, aforementioned coating layer has excellent water-repellancy and slipperiness as mentioned above, and to form be desirable to the outmost surface layer using aforementioned coating layer as functional panel.As aforementioned middle layer, be not particularly limited, can suitably select according to object, such as can list undercoat for improving the cementability of substrate layer and coating layer, for improving the ornament layer of having given pattern, color etc. of the designability of functional panel.
The functional panel of the present invention so obtaining is 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, adhering to of the various dirts that effectively to suppress to take incrustation scale be representative, even if use the strong clean-out system of pungency containing acid, alkali, be also difficult for producing rotten, deteriorated.In addition, even if use the such staining agent of hair dye, be also difficult for producing variable color, dyeing.Therefore, the suitable especially conduct of functional panel of the present invention is disposed at the bathroom of premises or the functional panel in kitchen.
< coating layer >
Photocurable resin composition of the present invention can be applied on base material, then make its photocuring, thereby on substrate layer, form coating layer.As the method for carrying out photocuring, conventionally there is the method for the light such as irradiation ultraviolet radiation.Face on the substrate layer of formation coating layer can be the only face in the middle of front and back, can be also these two faces, suitably selects as required.In addition, the irradiation dose of the light when Photocurable resin composition of the present invention is solidified is not particularly limited, and can suitably select according to object, while adopting ultraviolet ray, is 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 conventionally in several seconds～tens seconds.Owing to being cured so at short notice, therefore can realize the raising of the productivity of the functional panel obtaining.
Thickness as aforementioned coating layer, is not particularly limited, and can according to object, suitably be selected by the level of required designability, chemical proofing, is conventionally assumed to the thickness of the scope of 1 μ m～200 μ m.
In addition,, during irradiation ultraviolet radiation, ultraviolet curing reaction is free radical reaction, is therefore easily subject to the obstruction being caused by oxygen.Therefore, after aforementioned Photocurable resin composition is applied on base material, for fear of with the contacting of oxygen, also can under nitrogen atmosphere, said composition be solidified.In addition, the surface free energy by carrying out the coating layer that photocuring forms, from guaranteeing fully good water-repellancy and the viewpoint of slipperiness, is generally 12mJ/m 2～30mJ/m 2desirable.
< substrate layer >
Material as the substrate layer using in functional panel of the present invention, is not particularly limited, and can suitably select according to object, such as listing 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, be preferably material, the so-called FRP (fibre reinforced plastics) of fibers such as being added with glass fibre, carbon fiber in organic materials.As aforementioned FRP, be not particularly limited, can suitably select according to object, for example can list the sheet molding compound (SMC of the sheet that comprises unsaturated polyester resin, weighting agent and glass fibre or carbon fiber; Sheet molding compound), be the block bulk molding compound that the comprises staple fibre (BMC with the same matrix material of SMC; Bulk molding compound) etc.Aforementioned FRP normally obtains the compoundings such as heat-curing resin, organo-peroxide (solidifying agent), weighting agent, shrinking agent, internal mold release, reinforcement material, linking agent and thickening material, it is configured as and uses as the corresponding shape in place of building materials configuration by putting into mould the pressurization that is set as specified temperature.Wherein, if comprise unsaturated polyester as heat-curing resin, weighting agent and as the glass fibre of reinforcement material or the FRP of carbon fiber, can further improve the intensity of the functional panel integral body obtaining and weather resistance etc.
Aforementioned unsaturated polyester is generated by polyvalent alcohols such as the polyunsaturated polycarboxylic acids 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, can suitably select according to object, such as listing calcium carbonate, aluminium hydroxide etc.Wherein, from the viewpoint of cost, preferred calcium carbonate, from improving the viewpoint of the chemical proofing of FRP self, preferred aluminium hydroxide.Yet, as mentioned above, while forming aforementioned coating layer, as base material, even if adopt, use calcium carbonate as the FRP of weighting agent, also can improve fully the chemical proofing of functional panel integral body, therefore can easily realize the functional panel having by the substrate layer that FRP forms cheaply.
About the glass fibre as aforementioned reinforcement material and carbon fiber, be not particularly limited, can suitably select according to object, suitable use staple length for 20mm～50mm left and right, Fibre diameter be the fiber of 5 μ m～25 μ m left and right, it is desirable in FRP, with the amount of 10 quality %～70 quality %, containing.The aforementioned FRP as substrate layer mixes these compositions, with FRP manufacturing installation etc., manufactures and has the thickness of regulation and the FRP of size.
In addition, the thickness as aforementioned substrates layer, is not particularly limited, and can change according to the purposes of functional panel, more than being generally 2.5mm.The upper limit as the thickness of aforementioned substrates layer, is not particularly limited, and can suitably select according to object.
Embodiment
Below, enumerate embodiment and illustrate in greater detail the present invention, but the present invention is not subject to any restriction of following embodiment.
< Production Example 1>
By the polysiloxane polyhydric alcohol of 0.1mol number-average molecular weight 1000 (SILAPLANE FM-4411, general formula (2), p=1, q=3, (the total carbon number 5 of the R in general formula (1)), CHISSO CORPORATION manufacture), the polyoxyethylene glycol (PEG#1000, Japan Oil Co) of 0.1mol number-average molecular weight 1000 and 0.06g dibutyl tin laurate join in reaction vessel and stir.Then, at room temperature add 0.3mol isophorone diisocyanate (VESTANAT IPDI, Evonik Degussa GmbH manufactures).Be heated 70 ℃, under 300rpm, make its reaction 2.5 hours, obtain carbamate prepolymer solution.In the pre-polymer solution total amount obtaining, add 0.2mol pentaerythritol triacrylate (PE-3A, Kyoeisha Chemical Co., Ltd. manufactures), further stir 4 hours, reaction is finished, obtain dimethyl siloxane (methyl) origoester acrylate of number-average molecular weight approximately 3000.
< Production Example 2>
In Production Example 1, use the polysiloxane polyhydric alcohol (DMS-C16 of number-average molecular weight approximately 700, general formula (2), p=0, q=3, (the total carbon number 3 of the R in general formula (1)), the manufacture of Gelest company) replace using polysiloxane polyhydric alcohol (SILAPLANE FM-4411, general formula (2), the p=1 of number-average molecular weight 1000, q=3, (the total carbon number 5 of the R in general formula (1)), CHISSO CORPORATION manufactures), in addition, operate equally with Production Example 1, obtain dimethyl siloxane (methyl) origoester acrylate of number-average molecular weight approximately 3000.
< Production Example 3>
In Production Example 1, use the polysiloxane polyhydric alcohol (FM-4421 of number-average molecular weight approximately 5000, general formula (2), p=1, q=3, (the total carbon number 5 of the R in general formula (1)), CHISSO CORPORATION manufacture) replace using polysiloxane polyhydric alcohol (SILAPLANE FM-4411, general formula (2), the p=1 of number-average molecular weight 1000, q=3, (the total carbon number 5 of the R in general formula (1)), CHISSO CORPORATION manufactures), in addition, operate equally with Production Example 1, obtain dimethyl siloxane (methyl) origoester acrylate of number-average molecular weight approximately 7000.
< Production Example 4>
In Production Example 1, use the polysiloxane polyhydric alcohol (FM-4425 of number-average molecular weight approximately 10000, general formula (2), p=1, q=3, (the total carbon number 5 of the R in general formula (1)), CHISSO CORPORATION manufacture) replace using polysiloxane polyhydric alcohol (SILAPLANE FM-4411, general formula (2), the p=1 of number-average molecular weight 1000, q=3, (the total carbon number 5 of the R in general formula (1)), CHISSO CORPORATION manufactures), in addition, operate equally with Production Example 1, obtain dimethyl siloxane (methyl) origoester acrylate of number-average molecular weight approximately 12000.
< Production Example 5>
In Production Example 1, use the polysiloxane polyhydric alcohol (KF6001 of number-average molecular weight approximately 1700, general formula (2), p=1, q=3, (the total carbon number 5 of the R in general formula (1)), Shin-Etsu Chemial Co., Ltd's manufacture) replace using polysiloxane polyhydric alcohol (SILAPLANE FM-4411, general formula (2), the p=1 of number-average molecular weight 1000, q=3, (the total carbon number 5 of the R in general formula (1)), CHISSO CORPORATION manufactures), in addition, operate equally with Production Example 1, obtain dimethyl siloxane (methyl) origoester acrylate of number-average molecular weight approximately 4000.
< Production Example 6>
In Production Example 1, use the polysiloxane polyhydric alcohol (KF6002 of number-average molecular weight approximately 3000, general formula (2), p=1, q=3, (the total carbon number 5 of the R in general formula (1)), Shin-Etsu Chemial Co., Ltd's manufacture) replace using polysiloxane polyhydric alcohol (SILAPLANE FM-4411, general formula (2), the p=1 of number-average molecular weight 1000, q=3, (the total carbon number 5 of the R in general formula (1)), CHISSO CORPORATION manufactures), in addition, operate equally with Production Example 1, obtain dimethyl siloxane (methyl) origoester acrylate of number-average molecular weight approximately 5000.
< Production Example 7>
In Production Example 1, use the polysiloxane polyhydric alcohol (KF6003 of number-average molecular weight approximately 5500, general formula (2), p=1, q=3, (the total carbon number 5 of the R in general formula (1)), Shin-Etsu Chemial Co., Ltd's manufacture) replace using polysiloxane polyhydric alcohol (SILAPLANE FM-4411, general formula (2), the p=1 of number-average molecular weight 1000, q=3, (the total carbon number 5 of the R in general formula (1)), CHISSO CORPORATION manufactures), in addition, operate equally with Production Example 1, obtain dimethyl siloxane (methyl) origoester acrylate of number-average molecular weight approximately 7500.
< Production Example 8>
In Production Example 1, use the polysiloxane polyhydric alcohol (X-22-4952 of number-average molecular weight approximately 4000, general formula (2), p ≈ 5, q=3, (the total carbon number ≈ 13 of the R in general formula (1)), Shin-Etsu Chemial Co., Ltd's manufacture) replace using polysiloxane polyhydric alcohol (SILAPLANE FM-4411, general formula (2), the p=1 of number-average molecular weight 1000, q=3, (the total carbon number 5 of the R in general formula (1)), CHISSO CORPORATION manufactures), in addition, operate equally with Production Example 1, obtain dimethyl siloxane (methyl) origoester acrylate of number-average molecular weight approximately 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.'s manufacture) replace adding pentaerythritol triacrylate (PE-3A, Kyoeisha Chemical Co., Ltd. manufactures), in addition, operate equally with Production Example 1, obtain dimethyl siloxane (methyl) origoester acrylate of number-average molecular weight approximately 3000.
< Production Example 10>
In Production Example 1, add dipropylene glycol acrylate (trade(brand)name: DPGA, Di-ichi Kogyo Seiyaku Co., Ltd.'s manufacture) replace adding pentaerythritol triacrylate (PE-3A, Kyoeisha Chemical Co., Ltd. manufactures), in addition, operate equally with Production Example 1, obtain dimethyl siloxane (methyl) origoester acrylate of number-average molecular weight approximately 3000.
< Production Example 11>
In Production Example 1, add succsinic acid 2-acryloxy ethyl ester (trade(brand)name: A-SA, Xin Zhong village chemical industry society manufacture) and replace adding pentaerythritol triacrylate (PE-3A, Kyoeisha Chemical Co., Ltd. manufactures), in addition, operate equally with Production Example 1, obtain dimethyl siloxane (methyl) origoester acrylate of number-average molecular weight approximately 3000.
< Production Example 12>
In Production Example 1, interpolation replaces adding isophorone diisocyanate (VESTANAT IPDI as the hexamethylene diisocyanate (trade(brand)name: HDI, Evonik Degussa manufacture) in molecular structure without the polyisocyanate compound of cyclic skeleton, Evonik Degussa GmbH manufactures), in addition, operate equally with Production Example 1, obtain dimethyl siloxane (methyl) origoester acrylate of number-average molecular weight approximately 3000.
< Production Example 13>
In Production Example 1, polyoxyethylene glycol (the PEG#1000 that does not add number-average molecular weight 1000, Japan Oil Co), and add 0.2mol isophorone diisocyanate and replace adding 0.3mol isophorone diisocyanate, in addition, operate equally with Production Example 1, obtain dimethyl siloxane (methyl) origoester acrylate of number-average molecular weight approximately 2000.
< Production Example 14>
In Production Example 1, add 0.22mol isophorone diisocyanate and replace adding 0.3mol isophorone diisocyanate, in addition, operate equally with Production Example 1, obtain dimethyl siloxane (methyl) origoester acrylate of number-average molecular weight approximately 40000.
< Production Example 15>
In the silicone compounds one of polydimethylsiloxane terminal-modified one-tenth glycol being obtained in reaction vessel, at 30.0g [KCC of SHIN-ETSU HANTOTAI manufactures, X-22-176DX], add 132.6g isobornyl acrylate, 0.03g dibutyl tin laurate and stir.Then, at room temperature add 3.14g hexamethylene diisocyanate (HDI) [Evonik Degussa GmbH manufacture].Be heated 50 ℃, under 100rpm, make its reaction 3 hours, obtain carbamate prepolymer solution.In the pre-polymer solution total amount obtaining, add 2.24g vinylformic acid 2-hydroxyl ethyl ester, further stir 6 hours, reaction is finished, obtain 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, prepare Photocurable resin composition.The Photocurable resin composition obtaining is applied to the upper surface of the base material being formed by FRP (DICMAT (registered trademark) 2415, DIC Chemical Co., Ltd manufactures) with thickness 20 μ m.Then, carry out UV irradiation (1000mW/cm 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 and just made after sample, after long duration test, refer in the water of 50 ℃ and flood after 50 hours.
(1) consistency
The evaluation of consistency is undertaken by visual.Consistency when to (B) the optical polymerism oligopolymer as matrix resin and/or (C) photopolymerization monomer adds (A) dimethyl siloxane (methyl) origoester acrylate according to the judgement of following benchmark.
Zero: transparent
△: thin gonorrhoea
*: dense gonorrhoea
(2) water-repellancy
The evaluation of water-repellancy is that the contact angle of measuring water carries out.Wherein, the mensuration of contact angle is used the DM-500 that consonance interface science Co., Ltd. manufactures.On base material, drip the water droplet of 1.5 μ L, measure the water contact angle just having dripped after rear and long duration test.Carry out 3 times and measure, the value using its mean value as contact angle.
(3) slipperiness
The evaluation of slipperiness is that carry out at the landing angle of measuring water.Wherein, DM-500 and the DM-SA that consonance interface science Co., Ltd. manufactures used in the evaluation of slipperiness.On base material, drip the water droplet of 30 μ L, with the speed of 7.5 degree/seconds, Stage microscope is tilted, water droplet is started to mobile angle as the value at landing angle.Carry out 2 times and measure, the value using its mean value as landing angle.
[table 1]
Figure BDA0000458512700000331
[table 2]
Figure BDA0000458512700000341
[table 3]
Figure BDA0000458512700000351
[table 4]
Figure BDA0000458512700000361
[table 5]
Figure BDA0000458512700000371
[table 6]
Figure BDA0000458512700000381
* 1 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) as the isophorone diisocyanate (IPDI) of isocyanic ester and (c) reaction of (methyl) acrylate monomer and dimethyl siloxane (methyl) origoester acrylate that obtains (Miwon company manufactures, " SIU1300 ", number-average molecular weight: approximately 7000, functional group's number 6)
* 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) as the isophorone diisocyanate (IPDI) of isocyanic ester and (c) reaction of (methyl) acrylate monomer and dimethyl siloxane (methyl) origoester acrylate that obtains (Miwon company manufactures, " SIU1500 ", number-average molecular weight: approximately 8000, functional group's number 10)
Dimethyl siloxane (methyl) origoester acrylate obtaining in * 3 Production Examples 1
* dimethyl siloxane (methyl) origoester acrylate obtaining in 3-2 Production Example 2
* dimethyl siloxane (methyl) origoester acrylate obtaining in 3-3 Production Example 3
* dimethyl siloxane (methyl) origoester acrylate obtaining in 3-4 Production Example 4
* dimethyl siloxane (methyl) origoester acrylate obtaining in 3-5 Production Example 5
* dimethyl siloxane (methyl) origoester acrylate obtaining in 3-6 Production Example 6
* dimethyl siloxane (methyl) origoester acrylate obtaining in 3-7 Production Example 7
* dimethyl siloxane (methyl) origoester acrylate obtaining in 3-8 Production Example 8
* dimethyl siloxane (methyl) origoester acrylate obtaining in 3-9 Production Example 9
* dimethyl siloxane (methyl) origoester acrylate obtaining in 3-10 Production Example 10
* dimethyl siloxane (methyl) origoester acrylate obtaining in 3-11 Production Example 11
* dimethyl siloxane (methyl) origoester acrylate obtaining in 3-12 Production Example 12
* dimethyl siloxane (methyl) origoester acrylate obtaining in 3-13 Production Example 13
* dimethyl siloxane (methyl) origoester acrylate obtaining in 3-14 Production Example 14
The siloxane oligomer obtaining 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 extraneous compound of claim shown in following general formula (3)
Figure BDA0000458512700000401
Wherein, in general formula (3), R represents alkyl, and Me represents methyl, and n represents arbitrary integer.Herein, R is made as alkyl in order to eliminate the reactivity of end, and the present invention is not had to essence contribution.
* 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 extraneous compound of claim shown in following general formula (4)
Figure BDA0000458512700000402
Wherein, in general formula (4), Me represents methyl, and n represents arbitrary integer.
* 7 by the synthetic urethane acrylate oligomer with 1,2-polyoxybutylene unit of 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 Xin Zhong village Industrial Co., Ltd manufacture, 2-acryloxy ethyl succinate, SP value=22.7 (J/cm 3) 0.5
* 10Ciba Specialty Chemicals manufactures, " IRGACURE184 ", 1-hydroxyl-cyclohexyl-benzophenone
< has the synthetic method > of the urethane acrylate oligomer of 1,2-polyoxybutylene unit
The potassium hydroxide of take makes 1mol propylene glycol (Kanto Kagaku K. K.'s manufacture) and 12mol butylene oxide ring carry out addition as catalyzer, at 110 ℃ of temperature of reaction, obtains polyvalent alcohol.In the reaction vessel that nitrogen ingress pipe, agitator and prolong are housed, drop into 2mol2 in this polyvalent alcohol, 4-tolylene diisocyanate makes its reaction 2 hours at 70 ℃.Then the dibutyl tin laurate as catalyzer that adds lentamente 4mol vinylformic acid 2-hydroxyl ethyl ester, trace, further at 70 ℃, make its reaction 15 hours, obtain the urethane acrylate oligomer containing 1,2-butyleneglycol unit of number-average molecular weight approximately 1500.
The value of the normal heptane degree of holding of the urethane acrylate oligomer with 1,2-polyoxybutylene unit obtaining is thus 1.0g/10g.
Result from embodiment and the comparative example of table 1～6, by use (A) make the polysiloxane polyhydric alcohol shown in (a) aforementioned formula (1), (b) isocyanic ester and (c) end have and can react dimethyl siloxane (methyl) origoester acrylate obtaining with (methyl) acrylate monomer of the functional group of isocyanate reaction, can access can be in long-time the Photocurable resin composition of raising water-repellancy and slipperiness.

Claims (10)

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 there is dimethyl siloxane (methyl) origoester acrylate that can react with (methyl) acrylate monomer of the functional group of isocyanate reaction and obtain;
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,
Figure FDA0000458512690000011
Wherein, in described general formula (1), n represents to take the optional integer of mode that the number-average molecular weight of described (A) dimethyl siloxane (methyl) origoester acrylate is 700～40000, and 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 isocyanate group in described (b) isocyanic ester and the equivalence ratio (isocyanate group/hydroxyl) of the hydroxyl in the polysiloxane polyhydric alcohol shown in described (a) general formula (1) are greater than 100/100 and be below 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. according to the Photocurable resin composition described in any one in claim 1～3, it 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 2the alkyl that represents the n valency of carbon number 5～20, n represents the integer in 1～4 scope.
5. according to the Photocurable resin composition described in any one in claim 1～4, it is characterized in that, described (B) optical polymerism oligopolymer is for having (methyl) origoester acrylate of 1,2-polyoxybutylene unit.
6. according to the Photocurable resin composition described in any one in claim 1～5, it is characterized in that, described (b) isocyanic ester is in molecular structure, to have the polyisocyanate compound of cyclic skeleton.
7. according to the Photocurable resin composition described in any one in claim 1～6, it is characterized in that, in described (c) (methyl) acrylate monomer can be hydroxyl with the functional group of isocyanic ester radical reaction.
8. according to the Photocurable resin composition described in any one in claim 1～7, it is characterized in that, with respect to described (B) optical polymerism oligopolymer and/or (C) total of photopolymerization monomer, the content of described (A) dimethyl siloxane (methyl) origoester acrylate is 0.05 quality %～10 quality %.
9.Yi Zhongshi district member, is characterized in that having:
Photocurable resin composition described in any one in claim 1～8 is solidified to the coating layer forming; And substrate layer.
10. a functional panel, is characterized in that, has:
Photocurable resin composition described in any one in claim 1～8 is solidified to the coating layer forming; And substrate layer.
CN201280035678.2A 2011-07-19 2012-07-19 Light-curing resin composition, and plumbing member and functional panel using same Expired - Fee Related CN103687882B (en)

Applications Claiming Priority (3)

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CN113302249A (en) * 2019-01-18 2021-08-24 积水化学工业株式会社 Light-moisture-curable resin composition and cured product
CN113302249B (en) * 2019-01-18 2023-07-07 积水化学工业株式会社 Photo-moisture curable resin composition and cured body

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