CN101646959B - Lens - Google Patents

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CN101646959B
CN101646959B CN2008800098939A CN200880009893A CN101646959B CN 101646959 B CN101646959 B CN 101646959B CN 2008800098939 A CN2008800098939 A CN 2008800098939A CN 200880009893 A CN200880009893 A CN 200880009893A CN 101646959 B CN101646959 B CN 101646959B
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general formula
expression
lens
silane
curable resin
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CN101646959A (en
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斋藤宪
安藤秀树
林敬一
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Nippon Steel Chemical and Materials Co Ltd
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Nippon Steel Chemical Co Ltd
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08F290/08—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 side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/44—Block-or graft-polymers containing polysiloxane sequences containing only polysiloxane sequences
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/58—Metal-containing linkages
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/041—Lenses
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/04—Prisms

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Silicon Polymers (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Disclosed is a lens having excellent injection moldability and cast moldability in addition to chemical resistance, heat resistance, low water absorption and impact resistance. Specifically disclosed is a lens obtained by curing a curable resin represented by the general formula (1) below and having a dense structural unit (A) composed of a metal oxide having a packing coefficient Kp, which is calculated by the calculation formula (2) below obtained from free volume fraction, of 0.68-0.8, and a sparse structural unit (B) having a packing coefficient Kp of less than 0.68 and containing an organic compound and an organic metal oxide. The curable resin has at least one unsaturated bond and an average molecular weight of 800-60,000, and the weight ratio between the structural units (A) and (B), namely (A)/(B) is 0.01-5.00; -{(A)-(B)m}n- (1) Kp = An*Vw*p/Mw (2).

Description

Lens
Technical field
The present invention is a kind of with the eyeglass lens to be main, as to remove laser optical systems such as viewing optical system, magneto optical driver such as projection optical systems such as image pickup optical systems such as camera, display device, the portrait display device lens, also can be used as the lens that optical elements such as lens or prism use that contain of in waveguide road etc. use; Specifically, relate to as except resistance to chemical reagents, thermotolerance, low water absorbable, impact resistance also with the optical material of the injection moulding property of excellence and moulding by casting property and preferred lens.
Background technology
Generally, organic glass is compared in light weight with unorganic glass, so the organic glass that is made up of the polymkeric substance of diglycol two (allyl carbonates), methyl methacrylate etc. is widely used.But the refractive index of these organic glass is 1.49～1.50, and is lower than unorganic glass (under the situation of white crown glass glass (white crown glass) is 1.523).Therefore, for the function of bringing into play regulation need be also thicker than the situation of unorganic glass, light-weighted advantage incurs loss.In addition, for example under the situation that the eyeglass lens that is used for vision correction uses, also there is the shortcoming of lens thickening, degraded appearance.
So in order to realize the improvement of refractive index, for example proposing to have used diallyl phthalate is the scheme of the organic glass etc. of monomer, but such organic glass generally is crisp, and the transmitance aspect also has problems.In order to improve this respect, also attempt diluting, but thermotolerance, the such performance of anti-solvent are produced obstacle with the simple function polymerizable monomer, need possess the research of the organic glass of enough performances.
On the other hand; In the optical element of laser optical systems such as the optical element of viewing optical systems such as the optical element of projection optical systems such as the optical element of image pickup optical systems such as camera, display device, portrait display device, magneto optical driver, waveguide road etc. in the optical elements such as the lens of use and prism; As most important key property, require in the use wavelength region may of used optical system, to have high photopermeability.And, in these optical elements, require high index of refraction property, low-birefringence property, thermotolerance, environment resistant, solvent resistance, high rigidity, mouldability etc. according to the condition of the kind of used optical system, optical property, shape etc.
In the past; As optical element; Except so-called to optical glass grind cut under attrition process or the high temperature the low-melting glass compression molding and the optical element of glass, generally also use with thermoplastic injection be shaped or with energy-curable type resin form, carry out polymerization with light and heat simultaneously and resinous optical element.Wherein optical glass is ground the optical element of cutting the glass that attrition process obtains and be difficult to the optics significant surface of this element is processed into the aspherical shape of receiving difference revisal excellent performance, exist owing to process the shortcoming that spended time is not suitable for producing in batches.With low-melting glass at high temperature carry out extrusion molding and the optical element of glass have optics significant surface with element be processed into aspherical shape than be easier to, low-birefringence and environment resistant etc. excellent limited, but do not wait the shaping of shape difficult at heavy caliber or big thickness, have shortcoming aspect the formability that other forming machine and mould price are high.
On the other hand, thermoplastic methacrylic resin has the character that engineering properties and shaping processability, weatherability etc. reach balance, is used in many aspects as sheet material or moulding material.And has the character of excellence on the optics such as the transparency, low dispersions, low-birefringence.
But there is the low such problem of high, the other thermotolerance of hydroscopicity in methacrylic resin.That is,,, so also exist based on commodity and the field that its use is restricted because moisture absorption produces the crack with dry prolonged and repeated circulation because moisture absorption produces the warpage of change in size, formed products.Particularly for be used for laser optical systems such as viewing optical system, magneto optical driver such as projection optical systems such as image pickup optical system, display device such as camera, portrait display device, for the lens of uses such as waveguide road etc., we can say that its influence is very big.In addition, because poor heat resistance also is restricted in uses such as vehicle-mounted purposes.And in recent years, because the densification of recording medium, the optical resin material of lens etc. is required further low-birefringenceization, also there is the inadequate field of birefringence of polymethylmethacrylate degree.
Therefore, in recent years, carried out the motion of One's name is legion about the optical property that keeps methacrylic resin, hygroscopic improvement simultaneously, stable on heating raising, low-birefringenceization etc.For example as giving the method for methacryl resin with low water absorbable, multipolymer (patent documentation 1), methyl methacrylate and cyclohexyl methacrylate and the benzyl methacrylate multipolymer (patent documentation 2) of propose to know clearly methyl methacrylate and cyclohexyl methacrylate.Though but exist low moisture absorptionization to improve but the shortcoming of thermotolerance reduction.In addition, as the method for giving thermotolerance, low-birefringence, the multipolymer (patent documentation 4) of multipolymer (patent documentation 3), methyl methacrylate and the maleimide compound of methyl methacrylate and o-methyl-phenyl-maleimide has been proposed.But, even, generally have the painted shortcoming that waits in this case owing to imported the maleimide monomer more.
Patent documentation 1: the spy opens clear 58-5318 communique
Patent documentation 2: the spy opens clear 58-13652 communique
Patent documentation 3: the spy opens clear 60-217216 communique
Patent documentation 4: the spy opens clear 61-95011 communique
Summary of the invention
The objective of the invention is to address this problem; A kind of lens are provided; Said lens can be used for the optical element of used lens in laser optical systems such as viewing optical system, magneto optical driver, waveguide roads etc. such as projection optical systems such as image pickup optical system, display device such as eyeglass lens material and prism, camera, portrait display device etc.; Except resistance to chemical reagents, thermotolerance, low water absorbable, impact resistance, also with injection moulding property, the cast molding property of excellence.
The method of dealing with problems
The inventor etc. further investigate for the problem that lens had that solves in the past; The result finds through the compact structure position that has different fractional free volumes in the molecular structure and the curable resin at open structure position are cured; Can obtain having light-weight characteristics excellences such as resistance to chemical reagents, thermotolerance, low water absorbable, impact resistance simultaneously; And can injection moulding, the lens of cast molding, accomplished the present invention.
That is, the present invention provides a kind of lens, it is characterized in that, with formula (III)
{(R 3R 4R 5SiO 1/2) j(R 6R 7XSiO 1/2) i}-[{(RSiO 3/2) w(MO 2) x(RXSiO) y(XMO 3/2) z}-{(R 6R 7SiO) k} m] n-{(O 1/2SiR 6R 7X) i(O 1/2SiR 3R 4R 5) j} (III)
(wherein, R and R 3～R 7Be (a)-R 1-OCO-CR 2=CH 2, (b)-R 1-CR 2=CH 2Or (c)-CH=CH 2Unsaturated group or alkyl, naphthenic base, cycloalkenyl group, phenyl, hydrogen atom, alkoxy or the alkyl siloxy of expression are at R and R 3～R 7In each substituting group each other can be identical or different, but among the R at least 1 be above-mentioned (a) and (b) or (c) in any one, R 1Expression alkylidene, alkylidene radical or phenylene, R 2The expression hydrogen or alkyl, M is a silicon atom, X is halogen atom or alkoxy.In addition, w is the number more than 4, and x, y and z are the numbers that satisfies w+x+y+z >=8, and j and i be 0 or 1, satisfy the integer of j+i=1, and k is the number more than 1, and m and n represent the integer more than 1.) curable resin of expression is cured the lens that form, the curable resin of general formula (III) is to make through with RSiX 3, MX 4Or their potpourri is hydrolyzed in the presence of acid or base catalyst and the cage modle silicone resin of condensation reaction and the expression of the formula (I) that obtains and through with R 3R 4R 5SiX, R 6R 7SiX 2Or their potpourri is hydrolyzed in the presence of acid or base catalyst with condensation reaction and the organo-silicon compound of the formula (II) that obtains expression carry out crosslinked or hydrolytic condensation obtains; Has at least one unsaturated link; Mean molecular weight is 800～60000; In addition; The weight ratio that the curable resin of general formula (III) has compact structure unit (A) and open structure unit (B), available formula (1) expression and structural unit (A)/(B) is 0.01～5.00; Activity coefficient (packing coefficient) Kp that utilizes following calculating formula (2) to try to achieve that calculates from fractional free volume of wherein said compact structure unit (A) is 0.68～0.8, is made up of metal oxide, the Kp less than 0.68 of said open structure unit (B), contains organism and organic metal oxide and constitutes.
-{(A)-(B) m} n- (1)
(wherein m and n represent the integer more than 1.)
Kp＝An·Vw·p/Mw (2)
[wherein An=Avogadro number, Vw=Van der Waals volume, p=density, Mw=molecular weight, Vw=∑ Va, Va=(4 π/3)/Ra 3-∑ (1/3) π hi 2(3Ra-hi), hi=Ra-(Ra 2+ di 2-Ri 2)/2di, Ra=atomic radius, Ri=bonded atom radius and di=interatomic disance.]
(RSiO 3/2) w(MO 2) x(RXSiO) y(XMO 3/2) z (I)
(R 3R 4R 5SiO 1/2) j(R 6R 7SiO) k(R 6R 7XSiO 1/2) i (II)
[wherein, R is (a)-R 1-OCO-CR 2=CH 2, (b)-R 1-CR 2=CH 2Or (c)-CH=CH 2Unsaturated group or alkyl, naphthenic base, cycloalkenyl group, phenyl, hydrogen atom, alkoxy or the alkyl siloxy of expression are at R and R 3～R 7In each substituting group can be the same or different each other, but among the R at least one be above-mentioned (a) and (b) or (c) in any one, R 1Expression alkylidene, alkylidene radical or phenylene, R 2The expression hydrogen or alkyl; In addition, R 3～R 7Be (a)-R 1-OCO-CR 2=CH 2, (b)-R 1-CR 2=CH 2Or (c)-CH=CH 2Unsaturated group, alkyl, naphthenic base, cycloalkenyl group, phenyl, hydrogen atom, alkoxy or the alkyl siloxy of expression; And M is silicon atom, and X is halogen atom or alkoxy; W is the integer more than 4, and x, y and z are the integers that satisfies w+x+y+z>=8; J and i be 0 or 1, satisfy the integer of j+i=1; And k is the number more than 1.]
Wherein, As stated; Compact structure unit (A) by removing of formula (I) the metal oxide position with three-dimensional polyhedral structure skeleton at organism position constitute; Open structure unit (B) is made up of the chain unit of the organic metal oxide of being represented by formula (II) and the organism position of general formula (I), is optimal way of the present invention.
(RSiO 3/2) w(MO 2) x(RXSiO) y(XMO 3/2) z (I)
(R 3R 4R 5SiO 1/2) j(R 6R 7SiO) k(R 6R 7XSiO 1/2) i (II)
[wherein, R is with (a)-R 1-OCO-CR 2=CH 2, (b)-R 1-CR 2=CH 2Or (c)-CH=CH 2Unsaturated group or alkyl, naphthenic base, cycloalkenyl group, phenyl, hydrogen atom, alkoxy or the alkyl siloxy of expression are at R and R 3～R 7Kind of each substituting group can be the same or different each other, but among the R at least 1 be above-mentioned (a) and (b) or (c) in any one, R 1Expression alkylidene, alkylidene radical or phenylene, R 2The expression hydrogen or alkyl.In addition, R 3～R 7Be (a)-R 1-OCO-CR 2=CH 2, (b)-R 1-CR 2=CH 2Or (c)-CH=CH 2Unsaturated group, alkyl, naphthenic base, cycloalkenyl group, phenyl, hydrogen atom, alkoxy or the alkyl siloxy of expression.And M is a silicon atom, and X is halogen atom or alkoxy.W is the integer more than 4, and x, y and z are the integers that satisfies w+x+y+z >=8, and j and i be 0 or 1, satisfy the integer of j+i=1.And k is the number more than 1.]
In addition, above-mentioned general formula (I) is by RSiX 3, MX 4Or the hydrolytic condensate of their potpourri (wherein R, M and X are identical with the situation of general formula (I)) formation, above-mentioned general formula (II) is by R 3R 4R 5SiX, R 6R 7SiX 2Or their potpourri (R wherein 3～R 7And X is identical with general formula (II)) hydrolysate or hydrolytic condensate formation, the X of general formula (I) and at least a portion and this hydrolysate or hydrolytic condensate bonding and form the structure position (B) of general formula (I) are optimal ways of the present invention.
In the present invention, also can in the curable resin of general formula (1) expression, cooperate the hydrosilylation catalyzer with and/or after radical initiator obtains hardening resin composition, make this hardening resin composition heat curing or photocuring and obtain lens.In addition, also can be in this hardening resin composition, further cooperate the compound that has at least 1 hydrosilane groups in the molecule or have compound or the two of unsaturated group.What explain is; So-called in the present invention lens; Be meant with eyeglass lens to be main; Except the lens of projection optical systems such as image pickup optical systems such as camera, display device, laser optical systems such as viewing optical system, magneto optical driver such as portrait display device etc., also can be used as the optical element that contains the lens that are useful on waveguide road etc. or prism etc. in addition and the lens that use, below sometimes these are referred to as lens.
The effect of invention
According to the present invention, can obtain having that high photopermeability has high index of refraction property simultaneously, low-birefringence is forthright, and in light weight, the lens that resistance to chemical reagents, thermotolerance, low water absorbable, impact resistance etc. are all excellent.Lens of the present invention in addition can obtain through injection moulding, cast molding, so processing characteristics is also very excellent.
Embodiment
The present invention below more specifically is described.
Curable resin of the present invention shown in above-mentioned general formula (1), has the molecular structure that compact structure unit (A) and open structure unit (B) constitute, and has at least one unsaturated link.Wherein, the activity coefficient Kp that compact structure unit (A) calculated by following calculating formula (2) is the material that 0.68～0.8 metal oxide constitutes, open structure unit (B) by activity coefficient Kp less than 0.68, contain organism and organic metal oxide and constitute.
About compact structure unit (A), preferably by removing of above-mentioned general formula (I) unit that constitutes, the metal oxide position with three-dimensional polyhedral structure skeleton at organism position.At this so-called organism position is among the R (organic group) in the general formula (I) and the position of metallic atom (being Si and M) bonding.In general formula (I), at least 1 of R can be to have by (a)-R 1-OCO-CR 2=CH 2, (b)-R 1-CR 2=CH 2Or (c)-CH=CH 2The organic group of the unsaturated group of expression.What explain is that a plurality of R of general formula (I) each other can be identical or different.
General formula (I) is the cage modle silicone resin that is made up of three-dimensional polyhedral structure skeleton and organic group R; As an one of which example; With the w in the general formula (I) be 8, x, y and z are 0 situation; W is 10, x, y and z are 0 situation, and the instantiation that w is 12, x, y and z are 0 structure is illustrated in following structural formula (3), (4) and (5).Wherein, the structural unit of general formula (I) expression is not limited to the unit of this structural formula (3), (4) and (5) expression.What explain is that the structure of these materials is known, and the structure of specific functional group is passed through X ray crystalline texture analytic representation.
Figure GSB00000715632000071
Above-mentioned general formula (I) can pass through RSiX 3Or MX 4More than one of the compound of expression are hydrolyzed in the presence of acid or base catalyst and condensation reaction obtains.Wherein, R, X and M have the implication identical with R, X and the M of general formula (I).Wherein, At least 1 is to have the above-mentioned (a) and (b) or (c) organic group of the unsaturated group of expression among the preferred R; If the object lesson of preferred unsaturated group is shown, the 3-methacryloxypropyl of can giving an example, 3-acryloyl-oxy propyl group, aryl, vinyl and styryl.X is the water-disintegrable base of halogen atom, alkoxy in addition, if object lesson is shown, but illustration chlorine, bromine, methoxyl, ethoxy, positive propoxy and isopropoxy.
If RSiX is shown 3Shown in the preferred example of compound, can enumerate trichlorosilane, methyl trichlorosilane, ethyl trichlorosilane, isopropyl trichlorosilane, butyl trichlorosilane, tert-butyl group trichlorosilane, cyclohexyl trichlorosilane, phenyl trichlorosilane, vinyl trichlorosilane, allyltrichlorosilane, styryl trichlorosilane, cyclohexenyl group trichlorosilane, trimethoxy silane, MTMS, ethyl trimethoxy silane, isopropyl trimethoxy silane, butyl trimethoxy silane, tert-butyl trimethoxy silane, cyclohexyl trimethoxy silane, phenyltrimethoxysila,e, vinyltrimethoxy silane, allyltrimethoxysilanis, styryl trimethoxy silane, cyclohexenyl group trimethoxy silane, triethoxysilane, MTES, ethyl triethoxysilane, isopropyl triethoxysilane, butyl triethoxysilane, tert-butyl group triethoxysilane, cyclohexyl triethoxysilane, phenyl triethoxysilane, VTES, allyltriethoxysilane, styryl triethoxysilane, cyclohexenyl group triethoxysilane, tripropoxy silane, methyl tripropoxy silane, ethyl tripropoxy silane, isopropyl tripropoxy silane, butyl tripropoxy silane, tert-butyl group tripropoxy silane, cyclohexyl tripropoxy silane, phenyl tripropoxy silane, vinyl tripropoxy silane, allyl tripropoxy silane, styryl tripropoxy silane, cyclohexenyl group tripropoxy silane, methacryloxy MTES, methacryloxy MTMS, 3-methacryloxypropyl trichlorosilane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl triethoxysilane, 3-acryloxy propyl trimethoxy silicane, 3-acryloxy propyltrichlorosilan etc.
In addition, M is silicon, germanium, titanium or zirconium.If MX wherein is shown 4Shown in the preferred example of compound, can enumerate tetrachloro silicane, tetramethoxy-silicane, tetraethoxysilane, tetrachloro germane, tetramethoxy germane, tetraethoxy germane, titanium ethanolate, titanium propanolate, isopropyl titanate, butanols titanium, titanium isobutoxide, ethanol zirconium, propyl alcohol zirconium, zirconium iso-propoxide, butanols zirconium, isobutyl alcohol zirconium etc.
Secondly, open structure unit (B) is by the organism position (or substituting group) of the residue of the three-dimensional polyhedral structure skeleton in the structural unit of having removed above-mentioned general formula (I) expression and the organic metal oxide of representing like above-mentioned general formula (II) (organo-silicon compound) with chain unit.In other words, comprise the position of from the structural unit of above-mentioned general formula (I) expression, removing compact structure unit (A) and the structural unit of above-mentioned general formula (II) expression.More specifically be described below, can comprise R 3R 4R 5SiX, R 6R 7SiX 2Or their potpourri (R wherein 3～R 7And X is identical with general formula (II)) the chain structure thing of organic metal oxide of general formula (II) of hydrolytic condensate; And at least a portion bonding of the organism position of general formula (I) [promptly having removed residue (or substituting group)] or X, thereby the structure position (B) of formation general formula (1) with the three-dimensional polyhedral structure skeleton in the structural unit of general formula (I) expression.Be general formula (1) the organism position a part also can and general formula (II) bonding, whole and general formula (II) bonding at organism position that also can general formula (1).Get into the chain unit of general formula (II) with the organism position of the general formula (I) of general formula (II) bonding.
The structural unit of above-mentioned general formula (II) expression can pass through R 3R 4R 5SiX or R 6R 7SiX 2More than one of the compound of expression are hydrolyzed in the presence of acid or base catalyst and obtain with condensation reaction.Wherein, R 3～R 7And the R of general formula (II) 3～R 7Same meaning.R 3～R 7A part be under the situation of unsaturated group, if preferred object lesson is shown, can enumerate 3-methacryloxypropyl, 3-acryloyl-oxy propyl group, aryl, vinyl and styryl.X is halogen atom or alkoxy, if object lesson is shown, can enumerate chlorine, bromine, methoxyl, ethoxy, positive propoxy and isopropoxy.
If R is shown 3R 4R 5The preferred example of compound shown in the SiX can be enumerated trimethyl chlorosilane, vinyl-dimethyl base chlorosilane, dimethylchlorosilane, phenyl dimethylchlorosilane, phenyl chlorosilane, chlorotriethyl silane, trivinyl chlorosilane, methyl divinyl chlorosilane, allyldimethylcholrosilane, 3-methyl acryloyl o-propyl dimethylchlorosilane, 3-acryloyl-oxy propyl-dimethyl chlorosilane, styryl dimethylchlorosilane, trimethyl methoxy silane, vinyl-dimethyl methoxylsilane, dimethyl methyl TMOS, phenyl dimethyl methyl TMOS, phenyl methoxy silane, triethyl methoxy silane, trivinyl methoxy silane, methyl divinyl methoxy silane, allyl dimethyl methoxylsilane, 3-methacryloxypropyl dimethyl methyl TMOS, 3-acryloyl-oxy propyl-dimethyl methoxy silane, styryl dimethyl methyl TMOS, trimethylethoxysilane, vinyl-dimethyl base oxethyl silane, dimethylethoxysilane, phenyl dimethylethoxysilane, phenyl ethoxy silane, triethyl-ethoxy-silicane alkane, trivinyl Ethoxysilane, methyl divinyl Ethoxysilane, allyl dimethyl base oxethyl silane, 3-methacryloxypropyl dimethylethoxysilane, 3-acryloyl-oxy propyl-dimethyl Ethoxysilane, styryl dimethylethoxysilane, trimethyl propoxyl group silane, vinyl-dimethyl base propoxyl group silane, dimethyl propylene TMOS, phenyl dimethyl propylene TMOS, phenyl propoxyl group silane, triethyl propoxyl group silane, trivinyl propoxyl group silane, methyl divinyl propoxyl group silane, allyl dimethyl base propoxyl group silane, 3-methacryloxypropyl dimethyl propylene TMOS, 3-acryloyl-oxy propyl-dimethyl propoxyl group silane, styryl dimethyl propylene TMOS, trimethyl isopropoxy silane, vinyl-dimethyl base isopropoxy silane, dimethyl isopropoxy silane, phenyl dimethyl isopropoxy silane, propyloxy phenyl TMOS, triethyl isopropoxy silane, trivinyl isopropoxy silane, methyl divinyl isopropoxy silane, allyl dimethyl base isopropoxy silane, 3-methacryloxypropyl dimethyl isopropoxy silane, 3-acryloyl-oxy propyl-dimethyl isopropoxy silane, styryl dimethyl isopropoxy silane etc.
In addition, if R is shown 6R 7SiX 2Shown in the preferred example of compound, can enumerate dimethyldichlorosilane, vinyl dimethyl dichlorosilane (DMCS), divinyl dichlorosilane, allyl methyl dichlorosilane, dimethyl dichlorosilane (DMCS), dichloromethyl phenylsilane, Methylethyl dichlorosilane, ethyl vinyl dichlorosilane, allyl ethyl dichlorosilane, styryl dimethyl dichlorosilane (DMCS), styryl ethyl dichlorosilane, 3-methacryloxypropyl dimethyl dichlorosilane (DMCS), dimethyldimethoxysil,ne, vinyl methyl dimethoxysilane, divinyl dimethoxy silane, allyl methyl dimethoxy silane, methyl dimethoxysilane, aminomethyl phenyl dimethoxy silane, Methylethyl dimethoxy silane, ethyl vinyl dimethoxy silane, allyl ethyl dimethoxy silane, styryl methyl dimethoxysilane, styryl ethyl dimethoxy silane, 3-methacryloxypropyl methyl dimethoxysilane, dimethyldiethoxysilane, vinyl methyldiethoxysilane, divinyl diethoxy silane, allyl methyl diethoxy silane, methyldiethoxysilane, aminomethyl phenyl diethoxy silane, Methylethyl diethoxy silane, ethyl vinyl diethoxy silane, allyl ethyl diethoxy silane, styryl methyldiethoxysilane, styryl ethyl diethoxy silane, 3-methacryloxypropyl methyldiethoxysilane, dimethyl dipropoxy silane, vinyl methyl dipropoxy silane, divinyl dipropoxy silane, allyl methyl dipropoxy silane, methyl dipropoxy silane, aminomethyl phenyl dipropoxy silane, Methylethyl dipropoxy silane, ethyl vinyl dipropoxy silane, allyl ethyl dipropoxy silane, styryl methyl dipropoxy silane, styryl ethyl dipropoxy silane, 3-methacryloxypropyl methyl dipropoxy silane, dimethyl diisopropoxy silane, vinyl methyl diisopropoxy silane, divinyl diisopropoxy silane, allyl methyl diisopropoxy silane, methyl diisopropoxy silane, aminomethyl phenyl diisopropoxy silane, Methylethyl diisopropoxy silane, ethyl vinyl diisopropoxy silane, allyl ethyl diisopropoxy silane, styryl methyl diisopropoxy silane, styryl ethyl diisopropoxy silane, 3-methacryloxypropyl methyl diisopropoxy silane etc.
Curable resin among the present invention can be through making above-mentioned general formula (I) expression the reactive organic silicon compound represented of cage modle silicone resin and general formula (II) obtain, the curable resin that obtains has the unsaturated link of the structural unit shown in above-mentioned general formula (I) and the above-mentioned general formula (II) through molecular structure crosslinked or that the hydrolytic condensation condensation forms.And this curable resin to have the activity coefficient Kp that calculates from fractional free volume be 0.68～0.8 the compact structure unit (A) and the open structure unit (B) of activity coefficient less than 0.68, and have at least one unsaturated link.
The calculating of the activity coefficient Kp that the present invention uses is calculated by following calculating formula (2).
Kp＝An·Vw·p/Mw (2)
(wherein An=Avogadro number, Vw=Van der Waals volume, p=density, Mw=molecular weight) wherein,
Vw＝∑Va
Va＝(4π/3)Ra 3-∑(1/3)πhi 2(3Ra-hi)
hi＝Ra-(Ra 2+di 2-Ri 2)/2di
(wherein Ra=atomic radius, Ri=bonded atom radius and di=interatomic disance)
In the calculating of above-mentioned activity coefficient Kp, atomic radius and interatomic disance use the chemical brief guide of Japanization association work basis to change the 3rd edition numerical value of being put down in writing.Be that atomic radius uses
Figure GSB00000715632000111
Interatomic disance uses
Figure GSB00000715632000112
Figure GSB00000715632000113
For example, the density of the glass represented of M=silicon atom, w=0, x=2, y=0 and the z=0 of general formula (I) is 2.23g/cm 3, its activity coefficient is 0.747.The R of general formula (I) is that the density of the prestox silsesquioxane with cube structure of methyl, w=8, x=0, y=0 and z=0 is 1.49g/cm 3, activity coefficient is 0.697.In addition, the R of general formula (II) 6And R 7For the density of the octamethylcy-clotetrasiloxane with ring texture of methyl, j=0, k=4 and i=0 is 0.956g/cm 3, its activity coefficient is 0.576.Same R 3And R 4, R 5, R 6And R 7For the density of the octamethyltrisiloxane with chain structure of methyl, j=2, k=1 and i=0 is 0.820g/cm 3, its activity coefficient is 0.521.Promptly, the activity coefficient of the metal oxide with three-dimensional polyhedral structure of silicon atom and three above oxygen atom bondings reaches more than 0.69 the compact structure unit among formation the present invention.The activity coefficient that has the compound of ring-type and chain structure in addition is 0.576 and 0.521, forms open structure of the present invention unit.
In addition, the compact structure unit (A) of curable resin of the present invention and the structural unit weight ratio (A)/(B) of open structure unit (B) are 0.01～5.00, are preferably 0.5～3.00.(A)/(B) very few less than compact structure under 0.01 the situation, mechanical properties and the thermotolerance that the lens that obtain are solidified in the curable resin shaping significantly worsened.Under the situation more than 5.00, it is very few with the open structure position of flexibility to give lens in addition, and toughness significantly worsens, becomes crisp lens.
In addition, the mean molecular weight of above-mentioned curable resin is 800～60000.Become fragile easily after being shaped during mean molecule quantity not sufficient 800, surpass 60000 o'clock curing molding processing difficulties on the contrary, bring inconvenience in the processing.What explain is that mean molecular weight can be measured through many GPC determinators of knowing.
As being used for RSiX 3Or MX 4The compound and the R of expression 3R 4R 5SiX or R 6R 7SiX 2The hydrolysis of the compound of expression and the acid catalyst of condensation can be enumerated hydrochloric acid and sulfuric acid.Also can these acid be mixed in addition and use, hydrolization group is under the situation of halogen atom, the hydrogen halides that generates in the time of also can utilizing hydrolysis.
As the base catalyst that is used for hydrolysis and condensation; But alkali metal hydroxides such as illustration potassium hydroxide, NaOH, cesium hydroxide, or ammonium hydroxide salt such as TMAH, tetraethyl ammonium hydroxide, TBAH, benzyltrimethylammonium hydroxide, benzyl triethyl ammonium ammonium hydroxide.In these materials, consider the preferred TMAH that uses from the high aspect of catalytic activity.Base catalyst uses as the WS usually.
Hydrolysis reaction must have water to exist, and this can be provided by the WS of catalyzer, also can be used as other purposes water and adds.The amount of water is to be enough to make more than the amount that hydrolization group is hydrolyzed, 1.0～1.5 times of preferred theoretical amount.
Method as at least a portion that makes general formula (I) and general formula (II) bonding has the R as the constituent of general formula (II) through manufacturing 3R 4R 5SiX or R 6R 7SiX 2Decomposability group and silanol group that can polycondensation etc. general formula (I), make R 3R 4R 5SiX or R 6R 7SiX 2With its reaction, bonding, can with fractional free volume in a part and compact structure unit (A) and open structure unit (B) distributed, be optimal way.
Manufacturing approach as the general formula (I) with silanol group etc. that can polycondensation can adopt to regulate to be used for RSiX 3Or MX 4Shown in compound hydrolysis-condensation reaction base catalysis dosage, control condensation reaction method and with RSiX 3Thereby the complete hydrolysis condensation, make the cage modle siloxane structure, make acid or base catalyst and its reaction cut off the method for the part of siloxane bonding.
In the manufacturing approach of general formula (I), exchange and save in RSiX with silanol group etc. that can polycondensation 3Or MX 4Shown in compound hydrolysis-condensation reaction base catalysis dosage, control condensation reaction method, below carry out concrete illustration.
If concrete illustration is used for the base catalyst of hydrolysis-condensation reaction, be ammonium hydroxide salt such as TMAH, tetraethyl ammonium hydroxide, TBAH, benzyltrimethylammonium hydroxide, benzyl triethyl ammonium ammonium hydroxide.Wherein consider the preferred TMAH that uses from the high aspect of catalytic activity.Base catalyst uses as the WS usually.
The use amount of base catalyst can be RSiX 3Or MX 4: base catalyst=4～10 mole: 1 mole.As long as in this scope, just can prevent the generation of the silsesquioxane compound of HMW, obtain the silsesquioxane of incomplete condensed type.If littler than this scope, then condensation reaction is fast, can cause gelation, if condensation reaction is suppressed at most, the remaining a lot of reactions of unreacted silanol group do not finish.
Hydrolysis reaction must have water to exist, and this can be provided by the WS of catalyzer, and the water that also can be used as other purposes adds.The amount of water is to be enough to make more than the amount of hydrolysising group hydrolysis, is preferably 1.0～1.5 times of theoretical amount.Hydrolization group will be remaining with unreacted state if this scope is little, if reaction is carried out causing gelation soon at most.
Preferably with an organic solvent, and consider preferably the two-phase system of polar solvent and non-polar solvent, to carry out from the viewpoint of reaction velocity control during decomposition as organic solvent.If concrete illustration polar solvent is for alcohols such as methyl alcohol, ethanol, 2-propyl alcohol etc.; The non-polar solvent of specifically giving an example is like toluene, xylene, benzene or the like.Wherein preferred 2-propyl alcohol and toluene.The volume ratio of polar solvent and non-polar solvent is preferably polar solvent/non-polar solvent=1/5～5/1, and more preferably 1/2.
For the hydrolysis reaction condition, temperature of reaction is preferably 0～60 ℃, more preferably 20～40 ℃.If temperature of reaction is lower than 0 ℃, then reaction velocity is slack-off, hydrolization group is remaining with unreacted state, form the result who consumes many reaction time.On the other hand, if be higher than 60 ℃, because reaction velocity is too fast, complicated condensation reaction is carried out, and the result has promoted the macromolecule of hydrolysate to quantize.In addition, the reaction time was preferably more than 2 hours.If reaction time less than 2 hours, hydrolysis reaction is insufficient to carry out, and forms hydrolization group to occur with the remaining state of unreacted state.
After hydrolysis reaction finishes; With the neutralization of slightly acidic water solution, this solution with washings such as saline solutions, is fully removed base catalyst and moisture and other impurity in the system; Carry out drying with drying agent such as anhydrous magnesium sulfates afterwards, can reclaim water-disintegrable product with methods such as decompression distillation.Preferred slightly acidic water solution is superfluous in order to neutralize fully adds.Mol ratio slightly acidic water solution with respect to base catalyst is preferably 1.0～1.5 times amount, more preferably 1.25 times amount.Even a small amount of, as long as base catalyst is remaining, remaining silanol group is with regard to reaction and macromolecule quantizes.Slightly acidic water solution can use the Dilution of sulphuric acid WS, hydrochloric acid dilute aqueous solution, citric acid dilute aqueous solution, aqueous acetic acid, aqueous ammonium chloride solution, aqueous solution of malic acid, phosphate aqueous solution, oxalic acid aqueous solution etc.
Secondly, but have in the method for general formula (I) of silanol group etc. of polycondensation, for RSiX in manufacturing 3The cage modle siloxane structure is made in the complete hydrolysis condensation, makes the concrete grammar of method of the part of acid or base catalyst and its reaction, cut-out siloxane bond, carries out illustration.
Make the cage modle silicone compounds in the presence of alkali compounds; In a kind of in non-polar solvent and polar solvent or the organic solvent that both are combined into; Cut off one or more siloxane bonds; Use keep cutting off end from the counter cation of alkali compounds after, through neutralization, with the hydroxy exchange, can make general formula (I) with silanol group etc.
Used alkali compounds when cutting off the siloxane bond of cage modle silicone compounds; For example can enumerate ammonium hydroxide salt such as TMAH, tetraethyl ammonium hydroxide, TBAH, benzyltrimethylammonium hydroxide, benzyl triethyl ammonium ammonium hydroxide, the monoacidic base metal hydroxides of lithium hydroxide, NaOH, potassium hydroxide etc.In these materials, from preferably ammonium hydroxide salt is effectively considered in performance as the effect of counter cation.The example of preferred ammonium hydroxide salt is a TMAH.With respect to 1 mole of cage modle siloxane structure unit, the use amount of alkali compounds can be 0.5～3 mole scope, more preferably can be 1.5～2.5 moles.In this when reaction, is not if 0.5 mole of the use amount deficiency of alkali compounds then reaction are carried out.On the other hand, decompose if surpass the cleacvage reaction of 3 moles then excessive promotion basket structure.Alkali compounds uses as alcoholic solution usually in addition.Alcoholic solution as using for example can be enumerated methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, wherein particular methanol.
Used organic solvent when cutting off the siloxane bond of cage modle silicone compounds can be a kind of in non-polar solvent and the polar solvent or organic solvent that both are combined into.If wherein non-polar solvent is illustrated object lesson, can enumerate hydrocarbon system solvents such as hexane, toluene, xylene, benzene etc.If non-polar solvent is illustrated object lesson, can have ether series solvents such as Anaesthetie Ether, tetrahydrofuran, ester series solvents such as ethyl acetate, pure series solvents such as methyl alcohol, ethanol, isopropyl alcohol, ketone series solvents such as acetone, methyl ethyl ketone etc.In these materials, bring the viewpoint of the control structure contribution that causes to consider, preferred polar solvent, wherein more preferably tetrahydrofuran from solvent and effect.
Reaction conditions when cutting off the siloxane bond of cage modle silicone compounds, temperature of reaction is preferably 0～60 ℃, more preferably 20～40 ℃.If temperature of reaction is lower than 0 ℃, reaction velocity is slack-off, can't carry out the cut-out of siloxane bond, forms the result who consumes a lot of reaction time.If be higher than 60 ℃ on the other hand, because reaction velocity is too fast, condensation reaction has also been carried out in the cut-out of the siloxane bond of dealing with complicated outward, and the result forms random structure, promotes macromolecule to quantize.About the reaction time,, normally several minutes to several hours, be advisable in 1～3 hour because of substituent R is different.
Reaction finishes back weakly acidic solution neutralization reaction solution.Become and divide after neutrality or the slant acidity dried up or contain the reaction dissolvent of water.Water or contain the separation of the reaction dissolvent of water can adopt this solution with washings such as saline solutions, fully remove moisture and other impurity, carries out methods such as drying afterwards with drying agent such as anhydrous magnesium sulfates.Use methods such as to adopt reduction vaporization under the situation of polar solvent, remove and add non-polar solvent behind the polar solvent, make that condensed polymer dissolving and above-mentioned is washed equally, drying.About the faintly acid solvent, can use Dilution of sulphuric acid solution, hydrochloric acid dilute solution, citric acid dilute solution, acetic acid, aqueous ammonium chloride solution, malic acid solution, oxalic acid solution etc.Non-polar solvent just can reclaim reaction product as long as separate with methods such as evaporations, if but non-polar solvent can be used as the non-polar solvent use of in ensuing reaction, using, just need it does not separated.
As making general formula (I) and R with silanol group etc. 3R 4R 5SiX or R 6R 7SiX 2The method of bonding; If for making X is that halogen atom, halogen atom are that the situation of the chlorosilane class bonding of chlorine is carried out illustration; A kind of in non-polar solvent and ether series solvent or made up in both solvent dissolved; The molal quantity with respect to the chlorine atom of chlorosilane class added the mixed liquor of amines such as the triethylamine more than 1 equivalent, pyridine aniline or the mixed liquor of alkali dissolution in amine series solvents such as pyridine, aniline of holding concurrently as solvent in; The general formula (I) that will contain silanol group etc. is dissolved in a kind of in non-polar solvent and the ether series solvent or has made up the solution that forms in both solvents; Under inert gas conditions such as nitrogen, drip under the room temperature, at room temperature carry out the stirring more than 2 hours afterwards.If at this moment the reaction time lacks, reaction does not sometimes finish.After reaction finishes, add toluene and water, the chlorosilane class of surplus, hydrochloric acid that subsidiary reaction generates and hydrochloride are dissolved in water layer and remove.In addition, also can utilize the method for removing through concentrating under reduced pressure with the dry organic layer of drying agent such as magnesium sulphate, with the alkali that uses and solvent.
In the present invention, also can in curable resin, cooperate hydrosilylation catalyzer or radical initiator or cooperate both and obtain hardening resin composition.Then this hardening resin composition is carried out heat curing or photocuring, carry out hydrosilylation, free radical polymerization, can obtain lens thus.In addition, except hydrosilylation catalyzer, radical initiator, further cooperate the compound that has unsaturated group in the compound that has at least one hydrosilane groups in the molecule, the molecule, also can obtain hardening resin composition.The purpose that promptly, obtain the purpose of lens from curable resin is solidified, the rerum natura of lens is improved is considered; As the adjuvant that promotes reaction, cooperate hydrosilylation catalyzer, thermal polymerization, thermal polymerization promoter, Photoepolymerizationinitiater initiater, light-initiated auxiliary agent, sensitizer etc. and obtain hardening resin composition.
Under the situation that cooperates the hydrosilylation catalyzer, with respect to the weight of curable resin, its addition adds with the scope of 1～1000ppm in metallic atom, preferably adds with 20～500ppm scope.In addition, as radical initiator, under the situation that cooperates Photoepolymerizationinitiater initiater or thermal polymerization, its addition is the scope of 0.1～5 weight portion with respect to curable resin 100 weight portions, more preferably the scope of 0.1～3 weight portion.If this addition less than 0.1 weight portion, curing becomes insufficient, the intensity of the lens that obtain, rigidity step-down.On the other hand, if surpass the problem that 5 weight portions just might produce lens coloring etc.Can use hydrosilylation catalyzer and radical initiator separately in addition, also can two or more and usefulness.
As the hydrosilylation catalyzer, platinum chloride (IV) saltization of can giving an example the 2nd platinum), platinum group metal series catalysts such as complex, dicarbapentaborane dichloro platinum and the palladium series catalyst of complex, platinum and the vinylsiloxane of complex, chlorination platinic acid and the olefines of chlorination platinic acid, chlorination platinic acid and alcohol, aldehyde, ketone, rhodium series catalysts.In these materials, consider the complex of complex, platinum and the vinylsiloxane of preferred chlorination platinic acid, chlorination platinic acid and olefines from the catalytic activity aspect.These can use separately in addition, also can more than 2 kinds and use.
Used Photoepolymerizationinitiater initiater when hardening resin composition is made Photocurable resin composition can suitably use compounds such as acetophenone system, styrax system, benzophenone series, チ オ キ サ Application ソ Application system, acylphosphine oxide system.Specifically can give an example trichloroacetophenone, diethoxy acetophenone, 1-phenyl-2-hydroxy-2-methyl propane-1-ketone, 1-hydroxycyclohexylphenylketone, 2-methyl isophthalic acid-(4-methylbenzene sulfenyl)-2-morpholino propane-1-ketone, benzoin methyl ether, benzyl dimethyl ketal, benzophenone, チ オ キ サ Application ソ Application, 2; 4,6-trimethylbenzoyl diphenyl phosphine oxide, aminomethyl phenyl glyoxylic ester, camphor, dibenzoyl, anthraquinone, michaelis ketone (ミ ヒ ラ one ケ ト Application) etc.In addition, also can also use with light-initiated auxiliary agent, the sensitizer of Photoepolymerizationinitiater initiater combination performance effect.
Thermal polymerization as above-mentioned purpose is used can preferably use various organic peroxides such as ketone peroxide system, peroxy ketal system, hydrogen peroxide system, dialkyl peroxide system, diacyl peroxide system, peroxy dicarbonate system, peroxyester system.But illustration cyclohexanone superoxide, 1 particularly; Two (the uncle's six peroxidating) cyclohexanone of 1-, cumene hydroperoxide, dicumyl peroxide, benzoyl peroxide, diisopropyl superoxide, tert-butyl hydroperoxide-2 ethyl hexanoic acid ester etc., but be not limited thereto.In addition, these thermal polymerizations can use separately, also can mix use more than 2 kinds.
Curable resin is being made under the situation of hardening resin composition, but the compound that has at least 1 hydrosilane groups in the molecule that in curable resin, cooperates is oligomer and the monomer that has hydrogen at least on the silicon atom of the hydrosilylation more than 1 in molecule.As the oligomer that contains hydrogen atom on the silicon atom, can enumerate poly-hydrogen siloxane class, poly dimethyl hydrogen siloxy siloxane (Port リ ジ メ チ Le ヒ ロ De シ ロ キ シ シ ロ キ サ Application) type and multipolymer thereof, the terminal siloxane of having been modified by the dimethyl hydrogen siloxy.In addition; As the monomer that has hydrogen atom on the silicon atom; Can the illustration tetramethyl-ring tetrasiloxane, pentamethyl ring penta annular siloxane class, dihydro disiloxane class, three hydrogen list silanes, dihydro list silanes, a hydrogen list silanes, dimethyl silane oxygen radical siloxane classes etc. such as (ペ Application タ メ チ Le シ Network ロ ペ Application タ), also can mix more than 2 kinds.
The compound with unsaturated group that in curable resin, cooperates in addition, the repeat number that roughly is divided into structural unit are reactive oligomers and the low-molecular-weight of about 2～20 polymkeric substance, low viscous reactive monomer.In addition, roughly be divided into simple function unsaturated compound and have the multifunctional unsaturated compound more than 2 with a unsaturated group.
As reactive oligomers, can illustration polyvinyl siloxane class, poly dimethyl vinyl siloxy siloxane class and multipolymer thereof, the terminal type siloxane of having modified with dimethylvinylsiloxy, epoxy acrylate, epoxidized oil acrylic ester, urethane acrylate, unsaturated polyester (UP), polyester acrylate, polyether acrylate, vinylacrylic acid ester, polyene/mercaptan, organic silicon acrylic ester, polybutadiene, polystyrene-based ethyl-methyl acrylic ester etc.Simple function unsaturated compound and multifunctional unsaturated compound are arranged in these materials.
As reactive monofunctional monomer; Can illustration triethyl vinyl silanes, vinyl substituted silicon compound class such as triphenyl vinyl silanes; Cyclic olefins such as cyclohexene, styrene, vinyl acetate, N-vinyl pyrrolidone, butylacrylic acid ester, 2-ethylhexyl acrylate, n-hexyl acrylic ester, cyclohexyl acrylic ester, positive decyl acrylic ester, different isoborneol acrylic ester, two cyclopentene oxygen base ethyl propylene acid esters, phenoxyethyl acrylate, trifluoroethyl methacrylate etc.
As reactive polyfunctional monomer; Can illustration tetrem thiazolinyl silane, acetylene-derivatives such as vinyl substituted ring-type silicon compounds such as vinyl substituted silicon compound, tetramethyl tetrem thiazolinyl cyclotetrasiloxane, pentamethyl five vinyl D5s, two (TMS) acetylene, dibenzenyl such as divinyl tetramethyl disiloxane; Cyclic polyolefin classes such as norbornadiene, bicyclopentadiene, cyclo-octadiene; The ethene substituted cyclic alkene of VCH etc.; Divinylbenzene class, diacetylene-benzene class, trimethylolpropane allyl ether, pentaerythritol triallyl ether, tripropylene glycol diacrylate, 1,6 hexanediol diacrylate, biphenol A diglycidyl ether diacrylate, tetraethylene glycol diacrylate, 3-hydroxypivalic acid neopentylglycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol acrylate etc.
As the compound that has unsaturated group in the molecule, except above illustrative, can also use various reactive oligomers, monomer.In addition, these reactively oligomer, monomer can distinguish independent use, also can mix more than 2 kinds and to use.In addition, have in the molecule that uses among the present invention at least 1 hydrosilane groups compound, and molecule in have a unsaturated group compound can be used alone, can also be two or more kinds in combination respectively.
Can in the scope that does not break away from the object of the invention, add various adjuvants in the hardening resin composition.Can illustration as various adjuvants: organic/inorganic filler, plastifier, fire retardant, thermal stabilizer, anti-oxidant, light stabilizer, ultraviolet light absorber, lubricant, antistatic agent, release agent, gas-development agent, nuclear agent, colorant, crosslinking chemical, dispersing aid, resinous principle etc.
In the present invention, make its curing through heating or rayed, also can make lens, prism through the hardening resin composition that will contain any one or two kinds in hydrosilylation catalyzer, the radical initiator.Making through heating under the situation of multipolymer (formed body, i.e. lens, prism), its forming temperature is according to the selection of thermal polymerization and promoter, can in the wide scope about room temperature to 200 ℃, select.Under this situation, through in mould, on the steel band, making its polymerizing curable can obtain the formed body of desired shape.More specifically, injection moulding, extrusion molding, compression molding, transmission shaping, calendaring molding, casting (casting) these general shaping processing methods that are shaped can be used.
In addition, make through rayed under the situation of multipolymer (formed body),, can obtain formed body through the ultraviolet ray of illumination wavelength 100～400nm or the luminous ray of wavelength 400～700nm.Used light wavelength is not special to be limited, and is particularly suitable for using the near ultraviolet ray of wavelength 200～400nm.The lamp that uses as ultraviolet ray generation source can the illustration Cooper-Hewitt lamp (output power: 0.4～4W/cm), high-pressure mercury-vapor lamp (40～160W/cm), extra-high-pressure mercury vapour lamp (173～435W/cm), metal halide lamp (80～160W/cm), pulsed xenon lamp (80～120W/cm), electrodeless discharge lamp (80～120W/cm) etc.These UV-lamps have characteristic in beam split distribution separately, so will select according to the type of employed light trigger.
When processing lens of the present invention, prism, be suitable for injection moulding and cast molding usually.Specifically, be with added in hydrosilylation catalyzer, the radical initiator any one or this two kinds hardening resin composition enclose cylindrical shell, make its from cylindrical shell towards pre-heated mould through production line (line), to fixing mold injects, making the method for its curing by elastomeric seal pad or contained escapement.In addition, also make hardening resin composition pass through production line, to by rubber gasket or contained escapement and fixing mould injects, the method that in baking oven, is cured through heat.The method that in addition, also can adopt the mould made by transparent material to be cured through rayed.
In addition; When processing lens of the present invention, prism; Also can be as required to prevent reflecting, give high rigidity, improve abrasion performance, to give the purpose of the improvement of antifog property etc., implement physics or chemical processing such as surface grinding, electrostatic prevention processings, hard conating processing, bloomed coating processing, light modulation processing.
Below, embodiments of the invention are shown.What explain is that the curable resin that uses among the following embodiment is to obtain with the method shown in the following synthetic example.
Synthetic example 1
In 4 mouthfuls of flasks of the 2L with stirring machine, tap funnel, the tetramethylammonium hydroxide aqueous solution of the 20w% of pack into 300mL isopropyl alcohol, 600mL toluene and 22.37g (TMAH 4.55g/0.05mol, water 17.82g/0.99mol).In tap funnel, pack into the vinyltrimethoxy silane of 44.4g/0.30mol and the mixed solution of isopropyl alcohol 50mL, on one side the stirring reaction container, at room temperature dripped 3 hours on one side.Do not heat after drip finishing and stirred 3 hours.Stir after 3 hours, stop stirring and make reactant liquor slaking at room temperature 18 hours.The 0.1M aqueous citric acid solution that adds 1L in this reactant liquor is neutralized, after further water is washed to neutrality, adds anhydrous magnesium sulfate and dewater.Filter anhydrous magnesium sulfate, concentrate under the decompression.With the tetrahydrofuran 200mL dissolving of concentrate with dehydration, pack into have stirring machine, 4 mouthfuls of flasks of the 1L of tap funnel.In reaction vessel, add the pyridine 100mL of dehydration and in tap funnel, add phenylmethyldichloroislane 9.6g/0.05mol and phenyl dimethylchlorosilane 1.7g/0.01mol and tetrahydrofuran 30mL; Flow down stirring reaction container on one side at nitrogen, on one side under the room temperature with dropping in 3 hours.Do not heat after drip finishing and stirred 3 hours.Stir after 3 hours, behind the interpolation 30mL toluene, reaction solution is washed with water to neutrality, add anhydrous magnesium sulfate and dewater.Filter anhydrous magnesium sulfate, under reduced pressure concentrate, obtain curable resin A [general formula (1)] thus as the 30.1g of colourless transparent liquid.
In the 1H-NMR of this curable resin A,, therefore can confirm that the hydrolytic condensate from vinyltrimethoxy silane is a cagelike structure owing to can observe the signal of the distinctness of vinyl.Thus for metal oxide, promptly as the compact structure position (A) of the three-dimensional polyhedral structure that constitutes by Si oxide, can suppose by 8 silicon atoms and 12 (SiO that oxygen atom constitutes 3/2) 8The cube structure of expression, the Kp that derives is 0.73.In addition, (A) position in addition of above-mentioned curable resin is as (H 2C=CH-SiO 3/2) 8Vinyl and the (PhMe of residue 2SiO 1/2) and (PhMeSiO), be open structure position (B) that the weight ratio of obtaining thus [(A)/(B)] is 0.955, the number-average molecular weight Mn that is obtained by GPC is 6800.In addition, open structure unit (B) is by vinyl, (PhMe 2SiO 1/2) and (PhMeSiO) constitute, do not become three-dimensional polyhedral structure, Kp less than 0.69.What explain is, when calculating the Kp of compact structure unit (A), and (SiO 3/2) 8Be (A) part, exist therefore and can not take out as the part in general formula (I) resin, can not directly obtain Kp.Therefore as the little compound that is similar to of the influence of Kp is used (HSiO 3/2) 8Calculate.
Synthetic example 2
This synthesizes example and has structural formula (H with reference to special method manufacturing of opening 2004-143449 number open middle record 2C=CHSiO 3/2) nCage modle polyvinyl silsesquioxane.In reaction vessel, pack into as the 300mL isopropyl alcohol of solvent and 600mL toluene, as 5% tetramethylammonium hydroxide aqueous solution (TMAH 1.00g/0.01mol, the water 19.00g/1.06mol) 20g of base catalyst with stirring machine, tap funnel and thermometer.In tap funnel, add isopropyl alcohol 150mL and vinyltrimethoxy silane 51.0g/0.34mol, on one side stirring reaction container limit at 0 ℃ down with the aqueous isopropanol of 1 hour dropping vinyltrimethoxy silane.After vinyltrimethoxy silane drip to finish, slowly return room temperature, do not heat and stirred 6 hours.After the stirring, transfer to and have Dean-Stark, in the reaction vessel of cooling tube, add 300mL toluene, at 120 ℃, on one side dephlegmate, isopropyl alcohol to the refluxing toluene heating, carry out condensation reaction more on one side.Stirred 3 hours behind the refluxing toluene, return to the room temperature cessation reaction then.Water to neutralization, adds the reactant liquor washing anhydrous magnesium sulfate and dewaters.Filter anhydrous magnesium sulfate, concentrate, obtain the cage modle polyvinyl silsesquioxane of 24.5g thus as white powder.
Then, in having the reaction vessel of stirring machine, add the above-mentioned cage modle polyvinyl silsesquioxane 20g/ (H that obtains 2C=CHSiO 3/2) be scaled 0.25mol and tetrahydrofuran 600mL dissolves, add methanol solution (the tetramethyl oxyammonia 5.75g/0.063mol) 23g of 25% TMAH, stirring at room is 2 hours under nitrogen atmosphere.Stir after 2 hours, add 10% aqueous citric acid solution 100mL and toluene 200mL and neutralize.After extracting organic layer, it with distilled water washing 3 times, with saturated common salt water washing 2 times, is dewatered with anhydrous magnesium sulfate.Filter anhydrous magnesium sulfate; The white powder that has concentrated with tetrahydrofuran 400mL and pyridine 300mL dissolving; Transfer in the reaction vessel that possesses tap funnel; Flow down stirring on one side at nitrogen, Yi Bian at room temperature with the mixed solution that dripped the tetrahydrofuran 70mL of dimethyldichlorosilane 5.9g/0.046mol and trimethyl chlorosilane 0.9g/0.007mol in 3 hours.After dripping end, stirred 2 hours under the room temperature.Stir after 2 hours, add toluene 300mL, then reaction solution is washed to neutrality, add anhydrous magnesium sulfate and dewater.Filter anhydrous magnesium sulfate, concentrate under the decompression, obtain curable resin B [general formula (1)] 23.2g thus as colourless transparent liquid.
In the 1H-NMR of this curable resin B,, therefore can confirm that the hydrolytic condensate from vinyltrimethoxy silane is a cagelike structure owing to can observe the distinct signal of vinyl.Thus for by metal oxide, be the compact structure position (A) of the three-dimensional polyhedral structure that constitutes of Si oxide, can be assumed to be by 8 silicon atoms and 12 (SiO that oxygen atom constitutes 3/2) 8The cube structure of expression, the Kp that derives is 0.73.(A) position in addition of above-mentioned curable resin is as (H in addition 2C=CH-SiO 3/2) 8Vinyl and the (Me of residue 3SiO 1/2) and (Me 2SiO), be open structure position (B), the weight ratio of obtaining thus [(A)/(B)] is 1.213, the number-average molecular weight Mn that is obtained by GPC is 1240.In addition, open structure unit (B) comprises vinyl, (Me 3SiO 1/2) and (Me 2SiO), do not form three-dimensional polyhedral structure, Kp less than 0.69.What explain is, when calculating the Kp of compact structure unit (A), because (SiO 3/2) 8Be (A) part, exist as the part in general formula (I) resin, therefore can not take out, can not directly obtain Kp.Therefore use (HSiO as the compound that Kp is influenced less, can be similar to 3/2) 8Calculate.
Embodiment 1
Above-mentioned synthetic routine 1 " curable resin A " 100 weight portions that obtain and dicumyl peroxide (the system パ one Network ミ Le D of NOF Corp) 2 weight portions are mixed to evenly the formation hardening resin composition.With its flow into in the mould of glass plate group combination reaching thickness 2mm,, heated in following 2 hours at 100 ℃ following 1 hour, 120 ℃ following 1 hour, 140 ℃ following 1 hour, 160 ℃ following 1 hour, 180 ℃, obtain formed body (lens).
Embodiment 2
Hydrogenated methyl siloxane-phenyl methyl silicone copolymers (the system HPM-502 of ア ヅ マ Star Network ス Co., Ltd.) 71 weight portions and platinum-vinyl siloxane complex (the system SIP6830.3 of ア ヅ マ Star Network ス Co., Ltd.) 0.5 weight portion that above-mentioned synthetic routine 1 " curable resin A " 29 weight portions, terminal hydrogen of obtaining are modified are mixed to evenly the formation hardening resin composition.With its flow into in the mould of glass plate combination reaching thickness 2mm, heated in following 2 hours at 100 ℃ following 1 hour, 120 ℃ following 1 hour, 140 ℃ following 1 hour, 160 ℃ following 1 hour, 180 ℃, obtain formed body (lens).
Embodiment 3
Above-mentioned synthetic routine 1 " curable resin A " 58 weight portions, terminal hydrogen of obtaining are modified hydrogenated methyl siloxane-phenyl methyl silicone copolymers (the system HPM-502 of ア ヅ マ Star Network ス Co., Ltd.) 42 weight portions, dicumyl peroxide (the system パ one Network ミ Le D of NOF Corp) 2 weight portions and platinum-vinyl siloxane complex (the system SIP6830.3 of ア ヅ マ Star Network ス Co., Ltd.) 0.5 weight portion be mixed to evenly the formation hardening resin composition.With its flow into in the mould of glass plate combination reaching thickness 2mm, heated in following 2 hours at 100 ℃ following 1 hour, 120 ℃ following 1 hour, 140 ℃ following 1 hour, 160 ℃ following 1 hour, 180 ℃, obtain formed body (lens).
Embodiment 4
Above-mentioned synthetic routine 2 " curable resin B " 100 weight portions that obtain and dicumyl peroxide (the system パ one Network ミ Le D of NOF Corp) 2 weight portions are mixed to evenly the formation hardening resin composition.With its flow into in the mould of glass plate combination reaching thickness 2mm, heated in following 2 hours at 100 ℃ following 1 hour, 120 ℃ following 1 hour, 140 ℃ following 1 hour, 160 ℃ following 1 hour, 180 ℃, obtain formed body (lens).
Embodiment 5
Hydrogenated methyl siloxane-phenyl methyl silicone copolymers (the system HPM-502 of ア ヅ マ Star Network ス Co., Ltd.) 65 weight portions and platinum-vinyl siloxane complex (the system SIP6830.3 of ア ヅ マ Star Network ス Co., Ltd.) 0.5 weight portion that above-mentioned synthetic routine 2 " curable resin B " 35 weight portions, terminal hydrogen of obtaining are modified are mixed to evenly the formation hardening resin composition.With its flow into in the mould of glass plate combination reaching thickness 2mm, heated in following 2 hours at 100 ℃ following 1 hour, 120 ℃ following 1 hour, 140 ℃ following 1 hour, 160 ℃ following 1 hour, 180 ℃, obtain formed body (lens).
Embodiment 6
Hydrogenated methyl siloxane-phenyl methyl silicone copolymers (the system HPM-502 of ア ヅ マ Star Network ス Co., Ltd.) 38 weight portions, dicumyl peroxide (the system パ one Network ミ Le D of NOF Corp) 2 weight portions and platinum-vinyl siloxane complex (the system SIP6830.3 of ア ヅ マ Star Network ス Co., Ltd.) 0.5 weight portion that above-mentioned synthetic routine 2 " curable resin B " 62 weight portions, terminal hydrogen of obtaining are modified are mixed to evenly the formation hardening resin composition.With its flow into in the mould of glass plate combination reaching thickness 2mm, heated in following 2 hours at 100 ℃ following 1 hour, 120 ℃ following 1 hour, 140 ℃ following 1 hour, 160 ℃ following 1 hour, 180 ℃, obtain formed body (lens).
[comparative example 1]
Use methacrylic resin, the polymethylmethacrylate of the thickness 2mm that obtains processing through injection moulding.
The polymethylmethacrylate that formed body (lens) that obtains for the foregoing description and comparative example obtain carries out the evaluation of following each project.The result is shown in table 1.
1. refractive index: measure with Abbe refractometer (ア タ go system).
2. total light transmittance (with reference to specification JIS K 7361-1): the flat board that makes sample thickness 2mm is measured.
3. saturated water absorption: as test film, make the flat board of 50mm * 100mm * 2mm, 80 ℃ make its drying after, gravimetry then floods in 25 ℃ warm water to the weight of test film and reaches balance.Weight after the mensuration balance is obtained saturated water absorption through following formula.
Saturated water absorption (%)=[(suction weight-dry weight)/dry weight] * 100
4. drug-resistant test: in each medicine, sample was at room temperature soaked 48 hours, estimate weight change and outward appearance.Evaluation mark in the table is following:
Zero: weight change is less than 1w%, the basic no change of outward appearance
*: more than the weight change 1w%, outward appearance changes
5. thermotolerance: through dynamic thermomechanical analysis, be 5 ℃/min, and distance is measured glass transition temperature under the condition of 10mm between chuck at programming rate.
[table 1]
Figure GSB00000715632000251
In addition, the injection moulding test of in the foregoing description 1～6, making each hardening resin composition of formed body is carried out as follows.The hardening resin composition that will in embodiment 1～3, use is expelled to injection pressure 3Mpa in the mould of φ 5mm plano-convex lens, in pressurize: 1Mpa/10 second, mold temperature: carry out injection moulding under 180 ℃, each condition of 1 minute set time and obtain lens.Its result, under the situation of whole hardening resin composition of embodiment 1～3, outward appearance do not have peel off, wrinkle, crackle, good to the transfer printing property of mould in addition, good forming ability.

Claims (7)

1. lens is characterized in that, it is that the curable resin that formula (III) is represented is cured the lens that form,
{(R 3R 4R 5SiO 1/2) j(R 6R 7XSiO 1/2) i}-[{(RSiO 3/2) w(MO 2) x(RXSiO) y(XMO 3/2) z}-{(R 6R 7SiO) k} m] n-{(O 1/2SiR 6R 7X) i(O 1/2SiR 3R 4R 5) j} (III)
Wherein, R and R 3～R 7Be (a)-R 1-OCO-CR 2=CH 2, (b)-R 1-CR 2=CH 2Or (c)-CH=CH 2Unsaturated group or alkyl, naphthenic base, cycloalkenyl group, phenyl, hydrogen atom, alkoxy or the alkyl siloxy of expression are at R and R 3～R 7In, each substituting group can be the same or different each other, but among the R at least one be above-mentioned (a) and (b) or (c) in any one, R 1Expression alkylidene, alkylidene radical or phenylene, R 2The expression hydrogen or alkyl, M is a silicon atom, X is halogen atom or alkoxy; In addition, w is the number more than 4, and x, y and z are the numbers that satisfies w+x+y+z>=8, and j and i be 0 or 1, satisfy the integer of j+i=1; And k is the number more than 1, and m and n represent the integer more than 1;
The curable resin of general formula (III) is to make through with RSiX 3, MX 4Or their potpourri is hydrolyzed in the presence of acid or base catalyst and the cage modle silicone resin of condensation reaction and the expression of the formula (I) that obtains and through with R 3R 4R 5SiX, R 6R 7SiX 2Or their potpourri is hydrolyzed in the presence of acid or base catalyst with condensation reaction and the organo-silicon compound of the formula (II) that obtains expression carry out crosslinked or hydrolytic condensation obtains; Has at least one unsaturated link; Mean molecular weight is 800～60000; In addition; The curable resin of general formula (III) has compact structure unit (A) and open structure unit (B), available formula (1) expression, and the weight ratio of structural unit (A)/(B) is 0.01～5.00; The activity coefficient Kp that utilizes following calculating formula (2) to try to achieve that calculates from fractional free volume of wherein said compact structure unit (A) is 0.68～0.8, is made up of metal oxide, the Kp less than 0.68 of open structure unit (B), contains organism and organic metal oxide and constitutes;
-{(A)-(B) m} n- (1)
Wherein m and n represent the integer more than 1;
Kp＝An·Vw·p/Mw (2)
Wherein, An=Avogadro number, Vw=Van der Waals volume, p=density, Mw=molecular weight, Vw=∑ Va, Va=(4 π/3) Ra 3-∑ (1/3) π hi 2(3Ra-hi), hi=Ra-(Ra 2+ di 2-Ri 2)/2di, Ra=atomic radius, Ri=bonded atom radius and di=interatomic disance;
(RSiO 3/2) w(MO 2) x(RXSiO) y(XMO 3/2) z (I)
(R 3R 4R 5SiO 1/2) j(R 6R 7SiO) k(R 6R 7XSiO 1/2) i (II)
Wherein, R is (a)-R 1-OCO-CR 2=CH 2, (b)-R 1-CR 2=CH 2Or (c)-CH=CH 2Unsaturated group or alkyl, naphthenic base, cycloalkenyl group, phenyl, hydrogen atom, alkoxy or the alkyl siloxy of expression are at R and R 3～R 7In each substituting group can be the same or different each other, but among the R at least one be above-mentioned (a) and (b) or (c) in any one, R 1Expression alkylidene, alkylidene radical or phenylene, R 2The expression hydrogen or alkyl; In addition, R 3～R 7Be (a)-R 1-OCO-CR 2=CH 2, (b)-R 1-CR 2=CH 2Or (c)-CH=CH 2Unsaturated group, alkyl, naphthenic base, cycloalkenyl group, phenyl, hydrogen atom, alkoxy or the alkyl siloxy of expression; And M is silicon atom, and X is halogen atom or alkoxy; W is the integer more than 4, and x, y and z are the integers that satisfies w+x+y+z>=8; J and i be 0 or 1, satisfy the integer of j+i=1; And k is the number more than 1.
2. lens as claimed in claim 1; Wherein, Compact structure unit (A) by removing of above-mentioned general formula (I) the metal oxide position with three-dimensional polyhedral structure skeleton at organism position constitute the chain unit that open structure unit (B) is made up of the organic metal oxide of above-mentioned general formula (II) expression and the organism position formation of general formula (I).
3. according to claim 1 or claim 2 lens, wherein, general formula (II) is by R 3R 4R 5SiX, R 6R 7SiX 2Or the hydrolysate of their potpourri or hydrolytic condensate constitute, at least one bonding of the X in this hydrolysate or hydrolytic condensate and the general formula (I) and form the structural unit (B) of general formula (1), wherein R 3～R 7And X and general formula (II) is identical.
4. according to claim 1 or claim 2 lens wherein, cooperate hydrosilylation catalyzer and/or radical initiator in the curable resin of general formula (1) expression, obtain hardening resin composition after, this hardening resin composition is solidified forms.
5. lens as claimed in claim 3 wherein, cooperate hydrosilylation catalyzer and/or radical initiator in the curable resin of general formula (1) expression, obtain hardening resin composition after, this hardening resin composition is solidified forms.
6. lens as claimed in claim 4 wherein, further cooperate the compound that has at least 1 hydrosilane groups in the molecule and/or have the compound of unsaturated group and obtain hardening resin composition.
7. lens as claimed in claim 5 wherein, further cooperate the compound that has at least 1 hydrosilane groups in the molecule and/or have the compound of unsaturated group and obtain hardening resin composition.
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