CN104428331B - Active energy beam polymer resin composition and the laminated body for using the resin combination - Google Patents

Active energy beam polymer resin composition and the laminated body for using the resin combination Download PDF

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CN104428331B
CN104428331B CN201380036658.1A CN201380036658A CN104428331B CN 104428331 B CN104428331 B CN 104428331B CN 201380036658 A CN201380036658 A CN 201380036658A CN 104428331 B CN104428331 B CN 104428331B
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methyl
acid
acrylic acid
ester
resin combination
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CN104428331A (en
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石崎慎治
小出昌史
冈本淳二
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Toyochem Co Ltd
Artience Co Ltd
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Toyo Ink SC Holdings Co Ltd
Toyochem Co Ltd
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Priority claimed from JP2013029020A external-priority patent/JP5397558B1/en
Priority claimed from JP2013080718A external-priority patent/JP5417652B1/en
Application filed by Toyo Ink SC Holdings Co Ltd, Toyochem Co Ltd filed Critical Toyo Ink SC Holdings Co Ltd
Priority claimed from PCT/JP2013/068865 external-priority patent/WO2014010627A1/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • 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
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • 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
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • 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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking

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  • Optics & Photonics (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Paints Or Removers (AREA)

Abstract

A kind of active energy beam polymer resin composition is provided in the present invention, its heat resistance, humidity resistance, thermal dimensional stability and weatherability etc. are excellent, can suitably use in optical applications, and be substantially free of organic solvent, it is operational good, it is useful as smears or bonding agent.It constitutes using following substance as the active energy beam polymer resin composition of essential component, the essential component are as follows: intramolecular at least has 1 or more α, what β-unsaturated double-bond base oligomer (A), intramolecular had 1 or more carboxyl contains α, β-unsaturated double-bond compound (B) and cyclic imines (C1) or carbodiimide compound (C2).

Description

Active energy beam polymer resin composition and using the resin combination Laminated body
Technical field
The present invention relates to a kind of active energy beam polymer resin composition and use the stacking of the resin combination Body, specifically for the laminated body for being suitable for optical element purposes.
Background technique
Active energy beam polymer resin composition has polymerization speed fast, and generally can in solvent-free lower use, because This workability is excellent, and then the characteristics such as the energy level that needs is low when polymerizeing.Active energy beam polymer resin composition represents Property include: the resin component that can polymerize by active energy beam and there is α, β-unsaturated double-bond base monomer component. It is resin, poly- epoxy system resin and poly- using polyester based resin, polyurethane (polyurethane) as above-mentioned resin component The low molecular weights such as acrylic resin and molecular end have α, β-unsaturated double-bond base oligomer.By active energy beam Irradiation, above-mentioned monomer component and the common polymerization of above-mentioned resin component, and before polymerization terminates can be used as solvent and act as With.Therefore, above-mentioned active energy beam polymerizing resin has the advantages that without other solvent, therefore is formed in film Solvent volatilization occurs for Shi Buhui.
By above-mentioned viewpoint, by using above-mentioned active energy beam polymer resin composition, it is suitable for improving in recent years The problem of environmental pollution come, can be realized the reduction of environmental pollution.Therefore, active energy beam polymer resin composition is used for Include the electrical electricity such as the display devices such as architectural decoration material, packaging material, printing material and display material and optical device In the various fields of subassembly material, and it has widened tendency using field.
For example, above-mentioned resin combination can be used in bonding agent on the way in above-mentioned various fields.However, above-mentioned resin Composition and the adaptation of substrate (being applied face) are not necessarily good, therefore report the adaptation improved with various substrates Various methods.For example, in patent document 1, disclose by using specific saturation copolyester, and on changing at all The method for stating the molecular skeleton of above-mentioned oligomer in resin combination.In addition, in patent document 2, then disclosing in photocuring Property resin combination in cooperate α, β-unsaturated double-bond base end modifies the metal salt of phosphate as adaptation modifying agent Method.In addition, in patent document 3, disclosing the cooperation in Photocurable resin composition has tricyclic decenyl and α, β- The method of the compound of unsaturated double-bond base.
In addition, reactive oligomers class used in above-mentioned active energy beam polymer resin composition, it is general and Speech, viscosity is high, therefore as coating, the adhesive (binder) of bonding agent, it is difficult to individually operate.Therefore, generally by And with α, the reactive diluent of β-unsaturated double-bond base and low viscosity, to improve the operability as adhesive.As Above-mentioned reactive diluent, it is known that there are α, the multiple compounds (patent document 4 to 6) such as β-unsaturated double-bond base monomer.Its In, esters of acrylic acid generally shows excellent polymerism to active energy beam, therefore is extensively used.However, on the other hand, Foul smell and skin irritation are strong, therefore for coating or bonding agent containing esters of acrylic acid, it is expected that improving coating operations etc. makes The environment of used time.
On the other hand, in recent years, the prosperity and generalization comprising the information communication device including display are significant, are showing In the field of device, it is desirable that further increase the performance and productivity of the materials such as smears, bonding agent and sealing material.Then, As the material of display device, the various embodiments using above-mentioned active energy beam polymer resin composition are proposed.
In a display device, generally depending on the application and use to prevent the reflection from external light source anti-reflective film, To the various films such as protective film (protect film) for preventing display device surface damage to hurt.For example, as liquid crystal is constituted Show the liquid crystal cells component of device (LCD) and layered polarization plate, phase difference film.
In addition, flat-panel monitor (FPD) is not only used as display device, sometimes also to the function of its surface setting touch panel And it is used as input unit.In touch panel, also using films such as protective film, anti-reflective film and ITO vapor deposition resin films.
In above-mentioned film, it is representative be as component used for optical elements and use is in display device in the form of laminated body In.For example, above-mentioned film, be provided on its surface layer for preventing from damaging, preventing fingerprint attachment, antistatic or easy bondingization The coating layer being made of smears form using in a display device.In terms of other forms, above-mentioned film with across Bonding agent is attached at the form of the adherend such as optical element using in a display device.The smears that is used in the form of above-mentioned or Bonding agent requires the characteristic of the transparency or heat resistance etc first.For such requirement, in the art, generally use 2 liquid type heat curable adhesives or active energy beam polymerism using polyacrylic based resin as host agent and containing solvent are viscous Connect agent.
However, pervious active energy beam polymer resin composition, another although having many advantages, such as that polymerization speed is fast On the one hand but have the tendency that its polymer is difficult to obtain required substantially transparent property in optical applications.In addition, in use Resin combination is stated come when making laminated body used for optical elements, because the change in size characteristic of layers of material in laminated body is different, institute And have easily with temperature, humidity variation and the tendency that causes change in size, warpage (also referred to as crimp) to generate.In addition, above-mentioned Laminated body is preferably high refractive index, but in the composition of above-mentioned resin combination, it is difficult to adjust refractive index.Even if may make up The resin combination of high refractive index, the resin combination also have the tendency that lacking cementability.
Patent document 7 discloses the photopolymerization comprising polyurethane polyureas (methyl) acrylate and hydroxy acetophenone oligomer The Photocurable resin composition of initiator, contraction when which has curing rate fast and solidify is less and size The advantages of excellent in stability.However, the purposes for being defined in flooring material envelope using form of disclosed resin combination.By Patent document 7 is it is found that using above-mentioned resin combination as the protection smears of flooring material in use, can reduce flooring board The warpage of material.However, when above-mentioned resin combination is used for coated film use on the way, since the polymerization of above-mentioned resin combination is received Contracting is big, and can generate big warpage, it is difficult to have both the coating performances such as low crimpiness and adaptation.In addition, stating resin group in use Close object make 2 to 5 μm film coating layer in the case where, if be heated in curing process 120 DEG C or more and dry with Dry coating layer makes curing reaction then since heat when drying can make the Photoepolymerizationinitiater initiater in above-mentioned resin combination volatilize It is insufficient, have the tendency of coating variation.
In addition, patent document 8 and 9, which respectively discloses, to be made containing comprising sulphur atom and with α, β-unsaturated double-bond compound Active energy beam polymerizable composition, polymerizable composition polymerization obtained from high refractive index optical material.However, disclosed optical material, Bending adhesive strength (SA) according to JISK6856 is 0.1 hereinafter, lacking cementability.
In addition, being commonly by back side illuminaton liquid crystal layer and luminous backlight mode in the field of display device, represent Property is to be installed with the backlight unit (unit) of sidelight (edge lighting) type, full run-down type etc. in liquid crystal layer lower face side.It should Side light type backlight unit substantially has the wire el lamp as light source, the rectangular plate light guide plate along lamp end configuration, setting The light guide plate surface side light diffusing sheet and the prismatic lens of the piece surface side are set.Recently as light source, replace cold yin The situation of pole pipe (COFL) and the light emitting diode (LED) that uses color reprodubility, power saving excellent is more, along with this situation, Requirement to the heat resistance, dimensional stability of display device further increases.
As described above, in the field of display device, it is expected that exploitation not only has required by pervious advantage and optical applications Various characteristics also excellent active energy beam polymer resin composition.More specifically, seeking to be suitable as constituting light The smears of element laminated body or the active energy beam polymer resin composition of bonding agent are learned, the active energy beam is poly- Conjunction property resin combination is to be substantially free of organic solvent, and adaptation and excellent size stability when solidifying, and is reflected The resin combination of the excellent optical characteristics such as rate, full light transmittance and mist degree.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Application 56-95902 bulletin
Patent document 2: Japanese Unexamined Patent Application 57-180618 bulletin
Patent document 3: Japanese Unexamined Patent Application 57-87409 bulletin
Patent document 4: Japanese Unexamined Patent Publication 6-329731 bulletin
Patent document 5: Japanese Unexamined Patent Publication 2001-240609 bulletin
Patent document 6: Japanese Unexamined Patent Publication 2004-099644 bulletin
Patent document 7: Japanese Unexamined Patent Publication 08-27397 bulletin
Patent document 8: Japanese Unexamined Patent Publication 4-108816 bulletin
Patent document 9: Japanese Unexamined Patent Publication 5-271383 bulletin
Summary of the invention
Subject to be solved by the invention
In view of the above situation, the purpose of the present invention is to provide a kind of heat resistance, humidity resistance, thermal dimensional stability and Weatherability etc. is excellent, can suitably use in optical applications, and be substantially free of organic solvent, and operability is good, as painting Cloth agent or the useful active energy beam polymer resin composition of bonding agent.In addition, the object of the invention is also to provide one Kind laminated body is especially laminated body used for optical elements, which is to be especially at least the one of various optical films in various hyaline membranes There is the laminated body of resin layer constituted using above-mentioned resin combination on interarea, no matter and various optical films type such as What, above-mentioned resin layer can be bonded or coat easy and securely for the optical film, compared with former, in punching processing and wet It is more excellent in terms of heat durability.
The means to solve the problem
1st form of the invention is related to active energy beam polymer resin composition, and the feature of the resin combination is Include: intramolecular at least has 1 or more α, and β-unsaturated double-bond base oligomer (A), intramolecular have 1 or more carboxyl Containing α, β-unsaturated double-bond base compound monomer (B) and cyclic imines (C1) or carbodiimide compound (C2).
Above-mentioned resin combination preferably comprises the above-mentioned oligomer (A) of 1 to 99.8 parts by weight, 0.1 to 49.5 parts by weight It is above-mentioned to contain α, the above-mentioned cyclic imines of β-unsaturated double-bond base compound monomer (B) and 0.1 to 49.5 parts by weight (C1) or carbodiimide compound (C2).
In above-mentioned resin combination, above-mentioned oligomer (A) is preferably comprised selected from Polyester oligomer (a-1), polyurethane series It is at least one kind of in group composed by oligomer (a-2), poly- epoxy oligomer (a-3) and polyacrylic oligomer (a-4) The above oligomer.
In above-mentioned resin combination, the weight average molecular weight of above-mentioned oligomer (A) is preferably 300 to 30,000.
In above-mentioned resin combination, above-mentioned to contain α, the acid value of β-unsaturated double-bond base compound monomer (B) is preferably 100 To 1,000mg KOH/g.
In above-mentioned resin combination, above-mentioned cyclic imines (C1) be preferably intramolecular have 1 or more have 3 member rings The compound of the imide ring of structure.
In above-mentioned resin combination, above-mentioned carbodiimide compound (C2) is preferably that intramolecular has 1 or more carbon two sub- The compound of amine key base.
Above-mentioned resin combination preferably further contains α, the change of β-unsaturated double-bond base without carboxyl containing intramolecular Monomer adduct (D).
Above-mentioned resin combination preferably further contains active energy beam polymerization initiator (E), and above-mentioned active-energy The use level of ray polymerization initiator (E) relative to resin combination 100 parts by weight of total amount in 0.01 to 20 parts by weight model It encloses.
Above-mentioned resin combination preferably further contains silane compound (F).
Above-mentioned resin combination is preferred for active energy beam polymerism smears or active energy beam polymerism is viscous Connect the use of agent on the way.
2nd form of the invention be related to there is substrate and be arranged on an at least interarea for the substrate by resin combination The laminated body for the resin layer that object is constituted, it is characterized in that: above-mentioned resin combination is the resin combination of the 1st form of the invention Object.
In above-mentioned laminated body, above-mentioned substrate is preferably hyaline membrane.In addition, above-mentioned hyaline membrane is preferably selected from poly- acetyl group fibre Tie up prime system film, polynorbornene mesentery, polypropylene mesentery, polyacrylic acid mesentery, polycarbonate mesentery, polyester mesentery, polyethylene It is at least one kind of in group composed by alcohol mesentery and polyimides mesentery.
3rd form of the invention is related to the resin layer for having optical film and being arranged on an at least interarea for the optical film Laminated body used for optical elements, it is characterized in that: above-mentioned resin combination be the 1st form of the invention resin combination.
The effect of invention
According to the present invention, it is possible to provide the active energy beam polymer resin composition that can polymerize under low-light (level).Separately Outside, it is also possible according to the invention to provide by using above-mentioned resin combination as bonding agent or smears, and can be with optical film letter Just and securely bonding or closely sealed, and punching processing, heat resistance and the excellent laminated body of humidity resistance, specifically for excellent Laminated body used for optical elements.
Japanese Patent Application 2012-155928, December 27 in 2012 filed in disclosure of the invention and on July 11st, 2012 Japanese Patent Application 2012-285822 filed in day, 2 months 2013 Japanese Patent Applications filed in 18 days 2013-029020 and 2013 Japanese Patent Application 2013-080718 theme is related filed on April 8, in, and the disclosure of their specifications is whole and at this Using as reference in specification.
With embodiment
Hereinafter, being illustrated to embodiments of the present invention.
< active energy beam polymer resin composition >
Active energy beam polymer resin composition of the invention, it is characterized in that including: intramolecular at least have 1 with What upper α, β-unsaturated double-bond base oligomer (A), intramolecular had 1 or more carboxyl contains α, the change of β-unsaturated double-bond base Monomer adduct (B) and cyclic imines (C1) or carbodiimide compound (C2).
Wherein, so-called " active energy beam ", refers to comprising ultraviolet light, visible light, infrared ray, electron beam and radioactive ray The energy-ray that can provide the broad sense to energy necessary to the activation that chemically reacts.Active-energy of the invention is penetrated Line polymer resin composition (hereinafter referred to as " resin combination ") makes polymerization reaction by above-mentioned active energy beam is irradiated It carries out, forms solidfied material.It is not particularly limited, but in an embodiment of the invention, above-mentioned active energy beam preferably contains The light energy of ultraviolet light.
Hereinafter, the constituent to resin combination illustrates.
(A) ingredient:
In resin combination of the invention, above-mentioned oligomer (A) is at least with α, β-unsaturated double-bond base monomer Polymer and/or various compound addition α, β-obtained compound of unsaturated double-bond base, in the molecule have 1 or more α, β-unsaturated double-bond base.Above-mentioned oligomer can also have various functional groups in addition to α, β-unsaturated double-bond base outside.Of the invention In one embodiment, above-mentioned oligomer (A) includes selected from Polyester oligomer (a-1), polyurethane series oligomer (a-2), gathers At least one or more in group composed by epoxy oligomer (a-3) and polyacrylic oligomer (a-4), can be without special limit Surely these substances are used.
(a-1) Polyester oligomer
As above-mentioned Polyester oligomer (a-1), as long as having 1 or more ester bond person in main chain backbone is without special It limits.It may be, for example: by the hydroxyl and (methyl) in the end or polyester chain of polyacid and the obtained polyester of polyhydric alcohol What the aftermentioned ingredient such as acrylic acid and maleic acid (B) namely intramolecular had 1 or more carboxyl contains α, β-unsaturated double-bond base Compound carries out being esterified obtained compound.As another example, may be used are as follows: the hydroxyl in the end of polyester or polyester chain Base, with the aftermentioned intramolecular such as (methyl) 2-Hydroxy ethyl acrylate and (methyl) 2-hydroxypropyl acrylate have 1 with Upper hydroxyl contains α, and β-unsaturated double-bond base compound carries out being esterified obtained compound.As another example, may be used are as follows: By acid anhydrides, (methyl) glycidyl acrylate and obtained Polyester oligomer of compound at least with 1 hydroxyl etc..
As above-mentioned polyacid, can enumerate: fatty family, alicyclic ring family and aromatic system, it respectively can be without special limit Surely it uses.As fatty family polyacid, can more specifically enumerate: oxalic acid, malonic acid, succinic acid, adipic acid, decanedioic acid, Azelaic acid, suberic acid, maleic acid, chlorination maleic acid, fumaric acid, dodecanedioic acid, pimelic acid, citraconic acid, glutaric acid, clothing health These aliphatic dicarboxylic acids and its acid anhydrides can be used in acid, succinic anhydride, maleic anhydride etc..In addition, it is possible to use above-mentioned acid anhydrides Derivative.
For example, the concrete example as said derivative, can enumerate the compound of following record.
The derivative of succinic anhydride: methyl succinic acid anhydrides, 2,2- dimethyl succinic anhydride, butyl succinic anhydride, isobutyl group Succinic anhydride, hexyl succinic anhydride, octyl succinic anhydride, dodecenyl succinic anhydride and phenylsuccinic acid acid anhydride etc..
The derivative of glutaric anhydride: glutaric anhydride, 3- allyl glutaric anhydride, 2,4- dimethylated pentanedioic acid acid anhydride, 2,4- bis- Ethylglutaric acid acid anhydride, butyl glutaric anhydride and hexyl glutaric anhydride etc..
The derivative of maleic anhydride: 2- methyl maleic anhydride, 2,3- dimethyl maleic anhydride, butyl maleic anhydride, amyl Maleic anhydride, hexyl maleic anhydride, octyl maleic anhydride, decyl maleic anhydride, dodecyl malic acid acid anhydride, 2,3- dichloride horse Come acid anhydrides, phenylmaleic anhydride and 2,3- diphenyl maleic anhydride etc..
As alicyclic ring family polyacid, for example, the following alicyclic dicarboxylic acid lifted and its derivative etc. can be used.
It is saturated alicyclic dicarboxylic acid: binary acid, -1 α of cyclopropane, 2 α-dicarboxylic acids, -1 α of cyclopropane, 2 β-dicarboxylic acids, cyclopropyl - 1 β of alkane, 2 α-dicarboxylic acids, cyclobutane -1,2- dicarboxylic acids, -1 α of cyclobutane, 2 β-dicarboxylic acids, -1 α of cyclobutane, 3 β-dicarboxylic acids, ring - 1 α of butane, 3 α-dicarboxylic acids, -1 β of (1R)-pentamethylene, 2 α-dicarboxylic acids, trans-cyclopentane -1,3- dicarboxylic acids, (1 β, 2 β)-ring Pentane -1,3- dicarboxylic acids, (1 β, 3 β)-pentamethylene -1,3- dicarboxylic acids, (1S, 2S) -1,2- cyclopentane dicarboxylic acid, 1,2- hexamethylene Alkane dicarboxylic acids, 1,3- cyclohexane dicarboxylic acid, 1,4- cyclohexane dicarboxylic acid, 1,1- cycloheptane dicarboxylic acids, cubane -1,4- dicarboxyl Acid, 2,3- norbornane dicarboxylic acids, hexahydro terephthalic acid, hexahydro M-phthalic acid, hexahydrophthalic acid and tetrahydro neighbour's benzene Dioctyl phthalate etc..
With the unsaturated cycloaliphatic dicarboxylic acids of 1 or 2 unsaturated double-bond in ring: 1- cyclobutane -1,2- dicarboxylic acids, 3- ring Butene-1,2- dicarboxylic acids, 1- cyclopentene -1,2- dicarboxylic acids, 4- cyclopentene -1,3- dicarboxylic acids, 1- cyclohexene -1,2- dicarboxylic acids, 2- cyclohexene -1,2- dicarboxylic acids, 3- cyclohexene -1,2- dicarboxylic acids, 4- cyclohexene -1,3- dicarboxylic acids and 2,5- hexadiene -1 α, 4 α-dicarboxylic acids etc..
In addition, as alicyclic dicarboxylic acid's acid anhydride, it is possible to use hydrogenated phthalic anhydride derivative.As concrete example, example Following substance: derivative (3- methyl-hexahydrophthalic anhydride and the 4- methyl-six of hexahydrophthalic anhydride can such as be enumerated Hydrogen phthalic anhydride), the derivative of tetrabydrophthalic anhydride (1,2,3,6- tetrabydrophthalic anhydride, 3- methyl-1, 2,3,6- tetrabydrophthalic anhydride, 4- methyl-1,2,3,6- tetrabydrophthalic anhydride and methyl butene base -1,2,3,6- Tetrabydrophthalic anhydride etc.).
As aromatic system polyacid, more specifically, for example, the following aromatic dicarboxylic acid lifted or its acid can be used Acid anhydride.
Aromatic dicarboxylic acid: phthalic acid, M-phthalic acid, terephthalic acid (TPA), toluene dicarboxylic acids, 2,5- dimethyl Terephthalic acid (TPA), 2,2 '-diphenyl dicarboxylic acids, 4,4- diphenyl dicarboxylic acid, 1,4- naphthalene dicarboxylic acids, 2,6 naphthalene dicarboxylic acid, norbornene Dicarboxylic acids, diphenyl methane -4,4 '-dicarboxylic acids, phenyl indane dicarboxylic acids, 1,2- Azulene dicarboxylic acids, 1,3- Azulene dicarboxylic acids, 4, 5- Azulene dicarboxylic acids, (-) -1,3- acenaphthene dicarboxylic acids, 1,4- anthracene dicarboxylic acids, 1,5- anthracene dicarboxylic acids, 1,8- anthracene dicarboxylic acids, 2,3- anthracene two Carboxylic acid, 1,2- phenanthrene dicarboxylic acids, 4,5- phenanthrene dicarboxylic acids and 3,9- dicarboxylic acids etc..
Aromatic dicarboxylic acid acid anhydride: phthalic anhydride and 4- methyl nadic anhydride etc..
In addition, compound below: chlorendic anhydride can be enumerated as the anhydride that can be used as polyacid and use Special acid anhydrides (the 1,4,5,6,7,7-hexachloro-5-norbornene-2,3- in (chlorendic anhydride), sea Dicarboxylic anhydride), diphenyl dicarboxylic acid acid anhydride, carbic anhydride (Himic anhydride), methylene -1, 2,3,6- tetrabydrophthalic anhydride, methyl -3,6-endomethylene-1,2,3,6 tetrahydro phthalic anhydride, 1,2- hexamethylene Dicarboxylic anhydride, 1- cyclopentene -1,2- dicarboxylic anhydride, methylcyclohexene dicarboxylic anhydride, 1,8- naphthalene dicarboxylic acids acid anhydride and octahydro -1,3- Dioxo -4,5- isobenzofuran dicarboxylic anhydride etc..
In addition, the polynary of the lower molecular weight that number-average molecular weight (Mn) is about 50 to 500 can be enumerated as above-mentioned polyalcohol The polyalcohols for the higher molecular weight that alcohols and number-average molecular weight (Mn) are about 500 to 50,000, can not limit especially respectively System ground uses.
As the polyalcohols of lower molecular weight, more specifically, for example, following substance can be enumerated.
Aliphatic or ester ring type di-alcohols: ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, fourth two Alcohol, 3- methyl-1,5- pentane diol, 2,4- diethyl -1,5- pentane diol, 2- methyl-1,8- octane glycol, 3,3 '-dihydroxies Methyl heptane, 2- butyl -2- ethyl -1,3- propane diol, polyethylene oxide glycol (addition molal quantity is 10 or less), polycyclic Ethylene Oxide glycol (addition molal quantity is 10 or less), propane diol, 1,3- butanediol, 1,4- butanediol, 1,5- pentane two Alcohol, 1,6- hexane diol, 1,9- nonane glycol, neopentyl glycol, octane glycol, butyl ethyl pentane diol, 2- ethyl -1,3- oneself Alkane glycol, cyclohexane diol, cyclohexanedimethanol, Tricyclodecane Dimethanol, cyclopentadiene dimethanol and dimer diol etc..
Aromatic diol class: bis- (2- hydroxyl-oxethyl) benzene of 1,3-, bis- (2- hydroxyl-oxethyl) benzene of 1,2-, the bis- (2- of 1,4- Hydroxyl-oxethyl) benzene, 4,4 '-methylene biphenols, 4,4 '-(Asia 2- norborny) biphenols, 4,4 '-dihydroxy biphenols, O-, m- and p- dihydroxy benzenes, 4,4 '-isopropylidene phenol and the resulting add-on type bis-phenol of addition epoxyalkane on bis-phenol Deng.
In addition, the raw materials bisphenol as add-on type bis-phenol, can enumerate: bisphenol-A, Bisphenol F etc., as raw material epoxyalkane, It can enumerate: ethylene oxide, propylene oxide etc..
As the polyalcohols of higher molecular weight, more specifically, can enumerate: high-molecular-weight poly ester polyol, high molecular weight Polyamides polyols, high-molecular-weight polycarbonate polyalcohol and high molecular weight polyurethane polyalcohol.High-molecular-weight polycarbonate is more First alcohol can react to obtain by the dihydric alcohol of above-mentioned lower molecular weight with carbonic ester or phosgene (phosgene).
Above-mentioned high-molecular-weight poly ester polyol also can be used as commodity acquirement.
For example, the commodity as the manufacture of Japan's textile company, can enumerate following substance: Vylon GK640 (number-average molecular weight (hereinafter, being also recorded as " Mn ")=18,000, glass transition temperature (hereinafter, being also recorded as " Tg ")=79 DEG C, hydroxyl value=5, acid value < 4, linear type)；Vylon GK880 (Mn=18,000, Tg=84 DEG C, hydroxyl value=5, acid value < 4, linear type)；Vylon 300 (Mn=23,000, Tg=7 DEG C, hydroxyl value=5, acid value < 2, linear type)；Vylon 500 (Mn=23,000, Tg=4 DEG C, hydroxyl value =5, acid value < 2, linear type)；Vylon 560 (Mn=19,000, Tg=7 DEG C, hydroxyl value=8, acid value < 2, branching type)；And Vylon 630 (Mn=20,000, Tg=75 DEG C, hydroxyl value=5, acid value=1, linear type).
As the commodity of Unitika company manufacture, following substance can be enumerated: UE-3600 (Mn=20,000, Tg=75 DEG C, hydroxyl value=4, acid value=1)；UE-3690 (Mn=14,000, Tg=91 DEG C, hydroxyl value=8, acid value=1).
As the commodity of Kuraray company manufacture, can enumerate following substance: (Mn=1,000, hydroxyl value=112 are sour by P1010 Value < 0.5, linear liquid type)；P2010 (Mn=2,000, hydroxyl value=56, acid value < 0.5, linear liquid type)；P4010 (Mn= 4,000, hydroxyl value=28, acid value < 0.5, linear liquid type)；P5010 (Mn=5,000, hydroxyl value=22, acid value < 0.5, threadiness Liquid type)；P6010 (Mn=6,000, hydroxyl value=19, acid value < 0.5, linear liquid type)；P4050 (Mn=4,000, hydroxyl value= 28, acid value < 0.5, linear liquid type)；P6010 (Mn=6,000, hydroxyl value=19, acid value < 0.5, linear liquid type)； N4010 (Mn=4,000, hydroxyl value=28, acid value < 0.5, linear liquid type)；PNOA4014 (Mn=4,000, hydroxyl value=28, acid Value < 0.5, linear liquid type)；P2011 (Mn=2,000, hydroxyl value=56, acid value < 0.5, linear liquid type)；And P4011 (Mn =4,000, hydroxyl value=28, acid value < 0.5, linear liquid type).
As the commodity of consonance fermentation chemistry company manufacture, following substance: Kyowa Paul 2000BA (Mn=can be enumerated 2,000, hydroxyl value=58, acid value < 0.5, linear liquid type)；And Kyowa Paul 5000PA (Mn=5,000, hydroxyl value=22, Acid value < 0.5, linear liquid type) etc..
It as the commodity of above-mentioned superpolyamide polyalcohol, can enumerate: the TPAE of chemical conversion industry company of Fuji manufacture 617 (Mn=15,000, Tg=90 DEG C, hydroxyl value=16, acid value=1, linear type) etc..
It as the commodity of above-mentioned high-molecular-weight polycarbonate polyalcohol, can enumerate: the Oxymer of PERSTORP company manufacture N112 (Mn=1,000, Tg=60 DEG C, hydroxyl value=112, acid value < 0.5, linear type).
As the commodity of chemical company of Asahi Chemical Industry manufacture, following substance can be enumerated: PCDL-T5651 (Mn=1,000, hydroxyl It is worth=110, acid value < 0.05, linear liquid type)；CDL-T5652 (Mn=2,000, hydroxyl value=56, acid value < 0.05, threadiness Liquid type)；PCDL-T4671 (Mn=1,000, hydroxyl value=110, acid value < 0.05, linear liquid type)；And PCDL-T4672 (Mn=2,000, hydroxyl value=52, acid value < 0.05, linear liquid type).
As the commodity of Kuraray company manufacture, following substance can be enumerated: PMHC-1050 (Mn=1,000, hydroxyl value= 112, acid value < 0.5, linear liquid type)；PMHC-2050 (Mn=2,000, hydroxyl value=56, acid value < 0.5, linear liquid type)； C-1090 (Mn=1,000, hydroxyl value=112, acid value < 0.5, linear liquid type)；C-2090 (Mn=2,000, hydroxyl value=56, acid Value < 0.5, linear liquid type)；C-3090 (Mn=3,000, hydroxyl value=37, acid value < 0.5, linear liquid type)；C-4090(Mn =4,000, hydroxyl value=28, acid value < 0.5, linear liquid type)；C-5090 (Mn=5,000, hydroxyl value=22, acid value < 0.5, line Shape liquid type)；C-1065N (Mn=1,000, hydroxyl value=112, acid value < 0.5, linear liquid type)；C-2065N (Mn=2, 000, hydroxyl value=56, acid value < 0.5, linear liquid type)；C-1015N (Mn=1,000, hydroxyl value=112, acid value < 0.5, line Shape liquid type)；And C-2015N (Mn=2,000, hydroxyl value=56, acid value < 0.5, linear liquid type) etc..
Above-mentioned high molecular weight polyurethane polyalcohol also can be used as commodity acquirement.
Such as: as the commodity of Japan's textile company manufacture, following substance can be enumerated: Vylon UR1350 (Mn=30, 000, Tg=3 DEG C, hydroxyl value=46, acid value < 1, linear type)；Vylon UR1400 (Mn=40,000, Tg=83 DEG C, hydroxyl value= 2, acid value < 1, linear type)；Vylon UR3210 (Mn=40,000, Tg=-3 DEG C, hydroxyl value=3, acid value < 1, linear type)； Vylon UR5537 (Mn=20,000, Tg=34 DEG C, hydroxyl value=17, acid value < 1, linear type)；And Vylon UR9500 (Mn= 25,000, Tg=15 DEG C, hydroxyl value=5, acid value < 1, linear type).
As the commodity of Mitsui Chemicals polyurethane company manufacture, following substance can be enumerated: TAKELAC E158 (hydroxyl value= 20, acid value < 3)；TAKELAC E551T (hydroxyl value=30, acid value < 3)；And TAKELAC A2789 (hydroxyl value=10, acid value < 2) Deng.
In addition, making the lactones open loops such as polycaprolactone glycol, poly- (Beta-methyl-gamma-valerolactone) glycol, poly- valerolactone glycol It polymerize obtained polyester polyol etc., it is also possible to make above-mentioned high molecular weight polyols class.
(a-2) polyurethane series oligomer
Above-mentioned polyurethane series oligomer (a-2), can be make to have the compound of the above isocyanate group of at least one with it is aftermentioned Intramolecular has the α that contains of 1 or more hydroxyl, and β-unsaturated double-bond base compound reacts obtained compound.Furthermore conduct Another example, can are as follows: makes have the compound of at least one isocyanate group and the obtained end of above-mentioned polyol reaction different The carbamate prepolymer of cyanic acid ester group contains α, β-unsaturated double-bond base with what aftermentioned intramolecular had 1 or more hydroxyl Compound react obtained compound.As other examples, are as follows: make to have the compound of at least one isocyanate group with The obtained reaction product of polyol reaction, then reacted with the compound with the above amino of at least one, obtain chain elongation The carbamate prepolymer of terminal isocyanate group contains α, β-unsaturation with what aftermentioned intramolecular had 1 or more hydroxyl The compound of double bond base reacts obtained compound.Polyalcohol is the polyester polyol of the polyalcohols of higher molecular weight, packet It is contained in polyurethane series oligomer (a-2).In addition, isocyanate group is made to react the substance of the obtained base containing urea bond with amino Included in polyurethane series oligomer (a-2).
It can be simple function polyisocyanate and multifunctional isocyanic acid as the compound at least one isocyanate group Ester.It as specific compound, can enumerate: the poly- isocyanide of aromatic poly-isocyanate, aliphatic polymeric isocyanate, aromatic-aliphatic Acid esters, alicyclic polymeric isocyanate etc..
As the concrete example of simple function polyisocyanate, following substance can be enumerated: methyl isocyanate, ethyl isocyanate, different Propyl cyanate, butyl isocyanate, octyl isocyanate, isocyanic acid last of the ten Heavenly stems ester, isocyanic acid stearyl, isocyanic acid stearyl ester, isocyanide Sour cyclohexyl, phenyl isocyanate, benzyl mustard oil, p-chlorophenyl isocyanate, isocyanic acid p-nitrophenyl ester, isocyanic acid -2- chloroethene The chloro- 4- methyl phenyl ester of ester, isocyanic acid -2,4 dichloro benzene ester, isocyanic acid -3-, isocyanic acid tribromo-acetyl ester, isocyanic acid chlorine sulphonyl Ester, isocyanic acid-(R)-(+)-Alpha-Methyl benzyl ester, isocyanic acid-(S)-(-)-Alpha-Methyl benzyl ester, isocyanic acid-(R)-(-) -1- (1- naphthalene Base) ethyl ester, isocyanic acid-(R)-(+) -1- phenyl chlorocarbonate, isocyanic acid-(S)-(-) -1- phenyl chlorocarbonate and isocyanic acid be to toluene sulphur Acyl ester etc..
In polyfunctional isocyanate, as the concrete example of aromatic poly-isocyanate, can enumerate following substance: 1,3- is sub- Phenyl diisocyanate, 4,4 '-diphenyl diisocyanates, 1,4- phenylene vulcabond, 4,4 '-diphenyl methanes two Isocyanates, 2,4 toluene diisocyanate, 2,6- toluene di-isocyanate(TDI), 4,4 '-toluidine diisocyanates, Toluene-2,4-diisocyanate, 4,6- triisocyanate, benzene -1,3,5- triisocyanate, dimethoxyaniline diisocyanate, 4,4 '-diphenyl ether, two isocyanide Acid esters, 4,4 ', 4 "-triphenylmethane triisocyanates etc..
As the concrete example of aliphatic polymeric isocyanate, following substance: trimethylene diisocyanate, four methylenes can be enumerated Group diisocyanate, hexamethylene diisocyanate (alias: HDI), pentamethylene diisocyanate, two isocyanide of 1,2- propylidene Acid esters, 2,3- tetramethylene diisocyanate, 1,3- tetramethylene diisocyanate, ten dimethylene diisocyanates, 2,4,4- tri- Methyl hexamethylene diisocyanate etc..
As the concrete example of aromatic-aliphatic polyisocyanate, following substance: 1,3- dimethyl benzene-ω, ω '-can be enumerated Diisocyanate, 1,4- dimethyl benzene-ω, ω '-diisocyanate, 1,4- diethylbenzene-ω, ω '-diisocyanate, 1,4- Tetramethyl xylylene diisocyanate and 1,3- tetramethyl xylylene diisocyanate etc..
As the concrete example of alicyclic polymeric isocyanate, following substance: 3- isocyanatomethyl -3,5,5- tri- can be enumerated Isocyanatomethyl (alias: IPDI), 1,3- pentamethylene diisocyanate, 1,3- cyclohexane diisocyanate, 1,4- Cyclohexane diisocyanate, methyl -2,4- cyclohexane diisocyanate, methyl -2,6- cyclohexane diisocyanate, 4,4 '-Asias Methyl bis- (cyclohexyl isocyanates) and bis- (isocyanatomethyl) hexamethylenes of 1,4- etc..
In addition, a part as (a-2) ingredient, it can also be by 2- methylpentane -2,4- glycol of above-mentioned polyisocyanate Addition product and 3 polymers with isocyanurate ring etc. are used in combination.In addition, it is possible to use polyphenylene methane polyisocyanate is (not Name: PAPI), naphthalene diisocyanate and their polyisocyanate modifier etc..In addition, ester modified as polyisocyanate Object, it is possible to use there is carbodiimide, urea diketone (uretdione) base, urea imines (uretonimine) base, react with water Biuret (biuret) base, any group in isocyanurate group, or the modifier with two or more these group.It is right In the reactant of polyalcohol and diisocyanate, it is also possible to make the compound at least two isocyanate group.
In addition, the concrete example as the amine with amino, can enumerate following substance.
Monoamine: triethylamine, pyridine, aniline, morpholine, N-methylmorpholine, pyrrolidines, piperidines, N- methyl piperidine, hexamethylene Base amine, n-butylamine, dimethyl oxazoline, imidazoles, N- methylimidazole, N, N- dimethylethanolamine, N, N- diethyl ethylene diamine, N, N- dimethylisopro panolamine and N methyldiethanol amine etc..
It as aliphatic polyamine, can enumerate: ethylene diamine, trimethylene diamine, tetra-methylenedimine, pentamethylene two Amine, hexamethylene diamine, trien, diethylenetriamines, triaminopropane, 2,2,4- tri-methyl hexamethylene two Amine, 2,2,4- trimethylhexamethylenediamine, 2- hydroxyethyl ethylene diamine, hexamethylene diamine -2- hydroxyethyl Asia second Base diamines, N- (2- hydroxyethyl) trimethylene diamine, (2- hydroxyethyl propylidene) diamines, (two -2- hydroxyethyl ethylidene) Diamines, (two -2- hydroxyethyl propylidene) diamines, (2- hydroxypropyl ethylidene) diamines, (two -2- hydroxypropyl ethylidene) Diamines and piperazine etc..
Ester ring type polyamines: isophorone diamine and dicyclohexyl methyl hydride -4,4 '-diamines etc..
Aromatic diamine: phenylenediamine, xylylene diamine, 2,4- toluenediamine, 2,6- toluenediamine, diethyl first Phenylenediamine, 3,3 '-two chloro- 4,4 '-diaminodiphenyl-methanes, 4,4 '-bis- (sec-butyl) diphenyl methanes etc..
Possess the silicyl amine of simple function silicyl amino: for example, silicyl amine trimethyl silyl Dimethyl amine, trimethyl silyl diethylamide, dimethylamino trimethyl silane, allyl amino trimethyl silane, N- Methyl-N- trimethyl silylacetamide, anilino- trimethyl silane, 1- trimethyl silyl pyrroles, 1- trimethyl first Silylation pyrrolidones, 1- trimethyl-silyl-imidazole, 1- trimethyl silyl -1,2,4- triazole etc..
Possess the silicyl amine of 2 function silicyl amino: 1,1,3,3- tetramethyl-disilazane (silazane), hexamethyldisilazane, 1,3- divinyl -1,1,3,3- tetramethyl-disilazane and the bis- (front threes of N, N ' - Base silicyl)-N- phenylurea etc..
Possess 3 functions with the silicyl amine of upper annular silicyl amino: three silicon of 1,1,3,3,5,5- pregnancy basic ring Azane and 1,1,3,3,5,5,7,7- octamethylcyclotetrasilazane etc..
In addition, as the compound that can be used as above-mentioned amine and use, for example, following substance can be enumerated.
Aliphatic amine: 2,5- dimethyl -2,5- hexamethylene diamine and menthene diamines (menthenediamine) Deng bis- (the 2- amino-2-methyl propyl) piperazines of Isosorbide-5-Nitrae-；
The polypropylene glycol of amino is combined on the propylidene branched carbon of two end of molecule: as propylidene skeleton diamines Product " Jeffamine D230 " and " Jeffamine D400 " of the manufacture of San Techno chemical company etc., and as Asia third The product " Jeffamine T403 " etc. of the San Techno chemical company manufacture of base skeleton triamine,
Ethylene diamine, trimethylene diamine, butylene diamine, diethylenetriamines, trien, four ethylidene five Amine, penten, hexamethylene diamine, trimethylhexamethylenediamine, 1,2- diaminopropanes, iminobispropylamine, Methyl-imino double propylamine, 2,5- dimethyl -2,5- hexamethylene diamine；
The polypropylene glycol of amino is combined on the propylidene branched carbon of two end of molecule: as propylidene skeleton diamines Product " Jeffamine D230 " and " Jeffamine D400 " of the manufacture of San Techno chemical company etc., and as Asia third The product " Jeffamine T403 " etc. of the San Techno chemical company manufacture of base skeleton triamine；
Polyether skeleton diamines made of methylene: H is combined on the nitrogen of amine2N(CH2CH2O)2(CH2)2NH2 [San Techno chemical company manufacture ethylene glycol skeleton diamines " Jeffamine EDR148 "] etc. and 1,5- diamino -2- first Base pentane (" MPMD " of the manufacture of Japanese firm of Du Pont) etc.；
Cyclic amine: bis- (2- amino-2-methyl propyl) piperazines of N- aminoethylpiperazine, 1,4- etc.；
Amine containing aromatic ring: m-xylylenediamine (" MXDA " of the manufacture of Japanese firm of Du Pont) etc.；
The amine of amide-containing: daiamid (polyamide amine) (three and chemical company manufacture " X2000 ") Deng,
The bis- aminomethyl cyclohexanes of menthene diamines, isophorone diamine, 1,3- be (manufacture of gas chemical company of Mitsubishi " 1,3BAC "), 1- Cyclohexylamino -3- aminopropane, 3- amino methyl -3,3,5- Trimethyl-cyclohexyl amine；
Polyamines: dimethylene amine (" NBDA " that Mitsui Chemicals, Inc.'s system is made) of norbornane skeleton etc., by dimeric dibasic acid Carboxyl is converted to the dimer diamines of amino, end has the dendritic of primary or secondary amino；And
Alicyclic amines: two ends have the polyether polyols diamines etc. of propoxyl group amine.
(a-3) poly- epoxy oligomer
Poly- epoxy oligomer (a-3), be by compound with glycidyl, with (methyl) acrylic acid and Malaysia The aftermentioned ingredient such as acid (B), i.e., have the α that contains of 1 or more carboxyl with intramolecular, and β-unsaturated double-bond base compound (B) is anti- Answer resulting compound.As representative examples, it can enumerate: bisphenol type, epoxidation oil type, phenol novolak type and alicyclic ring type.Make For the poly- epoxy oligomer of bisphenol type, make bisphenols and the resulting bisphenol type diglycidyl of epichlorohydrin reaction Ether, the compound that resulting Mn400 to 2,000 is reacted with aftermentioned ingredients (B) such as (methyl) acrylic acid.
As epoxidation oil type polycyclic oxygen system oligomer, can be used through the oil such as epoxidized soybean oil and (methyl) The aftermentioned ingredient such as acrylic acid and maleic acid (B) reacts resulting compound.It, can as the poly- epoxy oligomer of phenolic varnish type Resulting compound is reacted using by phenolic resin varnish type epoxy resin, with aftermentioned ingredients (B) such as (methyl) acrylic acid.As The poly- epoxy oligomer of alicyclic ring type can be used anti-by aftermentioned ingredients (B) such as alicyclic type epoxy resin and (methyl) acrylic acid Answer synthesized compound.In addition, crosslink density when being polymerize to adjust using active energy beam, as needed, Intramolecular can also be used that there are multiple α, β-unsaturated double-bond base, others contain multifunctional α, β-unsaturated double-bond base chemical combination Object.
(a-4) polyacrylic oligomer
In the present invention, as oligomer (A), it is possible to use polyacrylic oligomer (a-4).As workable chemical combination The concrete example of object can be used and be selected from: have α, what β-unsaturated double-bond base modified polyether, amine were modified contains α, β-unsaturated double-bond The compound of base and in alkyd resin (alkyd resin), spiral shell acetal resin, polybutadiene, polymercaptan polyolefin tree Addition α on the various compounds such as rouge and polyalcohol, β-resulting modification of unsaturated double-bond base contain α, the change of β-unsaturated double-bond base Close the oligomer or prepolymer of one or more of group compound composed by object.
From agglutination density and with by the intermiscibility and heat resistance and wet-heat resisting for polymerizeing the other compositions to form film Property etc. can obtain good characteristic in terms of durabilities from the perspective of, the weight average molecular weight (hereinafter referred to as Mw) of above-mentioned oligomer (A) is excellent It is selected as 300 to 50,000 range, preferably 400 to 30,000 range.It is 50,000 oligomer below by using Mw, Can easily provide mobility it is excellent and with the intermiscibility of aftermentioned other compositions (B) and (C1) or (C2) also excellent resin group Close object.In addition, companion is as it does so, the drop of the films durability such as reduction and cementability of resin combination coating can be easily suppressed The bad situations such as low and film albefaction.On the other hand, the oligomer for being 300 or more by using Mw is using resin combination Object when being bonded film base material with adherend, is not susceptible to agglutination in adhesive layer as bonding agent and destroys.
It is not particularly limited, but in a currently preferred embodiment, above-mentioned oligomer (A) preferably at least contains (a- 2) polyurethane series oligomer.When above-mentioned resin combination is used on the way used in bonding agent etc., the elasticity and flexibility of adhesive layer have The key base depended in above-mentioned oligomer (A) and the tendency changed.When above-mentioned key base is the situation of ester or ether, it is easy to get Excellent flexibility.However, also flexible low and hydrolytic resistance also low tendency.On the other hand, ingredient (a- is stated in use 2) when, it is based on urethane bond, is easy to obtain the balance of elasticity with flexibility.In addition, mentioned component (a-2), due to water-fast Solution property is also good, therefore can easily improve water resistance, humidity resistance.In addition, in general, implementing sided corona treatment etc. to film When, there are carbonyls for film surface.For such carbonyl, above-mentioned urethane bond is easy to through the basic site due to nitrogen-atoms And it is formed to pole key (soda acid interaction), therefore can easily improve the adaptation and cementability to film.On the other hand, in key When base is the situation of ester or ether, the interaction with the carbonyl on above-mentioned film occurs between oxygen atom, is amino with key base The situation of formic acid esters is compared, and is weaker key.Actual situation, with identical match ratio modulation resin combination in, as upper Oligomer (A) is stated, using the situation of ingredient (a-2) compared with the situation using other compositions, in terms of various characteristics, is had The tendency of the former available more excellent result.However, in the present invention, even if stating the oligomer other than ingredient (a-2) in use When situation, by mating properly into other constituents, desired characteristic can also be readily derived.
(B) ingredient:
Secondly, there is the α that contains of 1 or more carboxyl for intramolecular, β-unsaturated double-bond base compound monomer (B) (with Under, referred to as compound monomer (B) or ingredient (B)) it is illustrated.In the present invention, mentioned component (B) is that intramolecular at least has 1 carboxyl, and at least contain 1 α, the monomer of β-unsaturated double-bond base compound.That is, the polymer as polymerizable monomer Above-mentioned oligomer (A) be not included in, the two distinguishes.Carboxyl in above compound monomer (B), with aftermentioned cyclic imide Reactive base in compound (C1) or carbodiimide compound (C2), performance acid-base reaction or opening etc. are mutual Effect.As a result, being formed due in above-mentioned interaction there are multiple α, β-unsaturated double-bond base is polyfunctional to contain α, and β-is no It is saturated double bond based compound, therefore the crosslink density of polymerizing curable film greatly improves.
As compound monomer (B), as long as to contain 1 or more carboxyl and 1 or more α, β-unsaturation in its structure The compound of double bond base, so that it may use with no particular limitation.It is not particularly limited, but as concrete example, chemical combination below can be enumerated Object.
Carboxylic fatty family contains α, β-unsaturated double-bond base carboxylic acids and its anhydride: (methyl) acrylic acid [acrylic acid is merged with methacrylic acid and is expressed as " (methyl) acrylic acid ".It is same as below], (methyl) acrylic acid -2- carboxyl Ethyl ester, (methyl) acrylic acid -2- carboxyl propyl ester, (methyl) acrylic acid -3- carboxyl propyl ester, (methyl) acrylic acid -4- carboxyl butyl ester, (methyl) acrylic acid dimer, maleic acid, fumaric acid, monomethyl maleic acid, monomethyl fumaric acid, aconitic acid, sorbic acid, cortex cinnamomi Acid, α-chlorination sorbic acid, glutaconate, citraconic acid, mesaconic acid, itaconic acid, tiglic acid, angelic acid, senecioic acid, crotonic acid, Iso-crotonic acid, mucobromic acid (mucobromic acid), mucochloric acid, sorbic acid, muconic acid (muconic acid), aconitic acid (aconitic acid), penicillic acid, geranic acid, citronellic acid, 4- acrylamide butane acid, 6- acrylamide hexane acid, amber Acid -2- (methyl) acryloyloxyethyl ester；By lactonic rings open loop additions such as list (methyl) acrylic acid-ω-carboxy-polycaprolactone esters Obtained end has polylactone system (methyl) acrylate of carboxyl；The epoxyalkane such as ethylene oxide, propylene oxide add repeatedly There is epoxyalkane addition system succinic acid and the ester of (methyl) acrylic acid etc. of carboxyl at obtained end.
It is carboxylic with alicyclic ring, aromatic ring contain α, β-unsaturated double-bond yl carboxylic acid class and its anhydride etc.: for example, hexahydro Phthalic acid -2- (methyl) acryloyloxyethyl ester, phthalic acid -2- (methyl) acryloyloxyethyl ester, O-phthalic Acid -2- (methyl) acryloxy propyl ester, phthalic acid -2- (methyl) acryloxy butyl ester, phthalic acid -2- (first Base) the own ester of acryloxy, phthalic acid -2- (methyl) acryloxy monooctyl ester, phthalic acid -2- (methyl) acryloyl Oxygroup last of the ten Heavenly stems ester, 2- vinyl benzoic acid, 3- vinyl benzoic acid, 4- vinyl benzoic acid, 4- isopropenyl benzene carboxylic acid, cortex cinnamomi Acid, 7- amino -3- vinyl -3- cephem -4- carboxylic acid (7-amino-3-vinyl-3-cephem-4-carboxylic Acid) etc..
Above compound can only use a kind, or multiple combinations are used can also.In an embodiment of the invention, make For above compound monomer (B), (methyl) acrylic acid and carboxylic (methyl) acrylate of intramolecular can be properly used.
Workable above compound monomer (B), obtains desired crosslink density by polymerizing curable film in the present invention Viewpoint is set out, preferably the acid value (hereinafter referred to as AV) of the range with 100 to 1,000mg KOH/g.AV be more preferably 150 to The range of 800mg KOH/g.When the AV of compound monomer (B) is 1,000mg KOH/g or less, it is easy that polymerizing curable is inhibited to apply The humidity resistance of film and the reduction of water resistance.In addition, when AV is 100mg KOH/g or more, due to above compound monomer (B), with the interaction of aftermentioned cyclic imines (C1) or carbodiimide compound (C2), it is easy to get preferable friendship Join density.With as it does so, when stating resin combination in use as smears, in the coating layer being made of resin combination In, it is easy to get the excellent durability such as heat resistance, humidity resistance.In addition, using resin combination as bonding agent, by film When substrate is attached in the adherend such as various substrates, the agglutination for being not susceptible to adhesive layer is destroyed.
Cyclic imines used in the present invention (C1) and carbodiimide compound (C2), respectively with above-mentionedization What the carboxyl of monomer adduct (B) interacted contains reactive nitrogen compound.It is above-mentioned containing reactive nitrogen compound, It is the acid-base reaction forming salt by carboxyl and nitrogen-atoms, the compound of addition reaction is on the other hand carried out with carboxyl.It is above-mentioned Addition reaction is promoted by irradiating active energy beam.Cyclic imines (C1) and carbodiimide compound (C2) It is specific as follows.
(C1) ingredient:
In the present invention, cyclic imines (C1) are that have chemical combination of 1 or more the cyclic imide base as reactive group Object, cyclic imide base can be closed with other key base junctions such as carbonyl, thiocarbonyl groups (thiocarbonyl).As concrete example, can enumerate: 3 The cricoid aziridine (also referred to as ethylene imine (aziridine)) of member, 4 yuan of cricoid azetidine (also referred to as azetidines (azetidine)), 5 yuan of cricoid pyrrolidines (also referred to as aza-cyclopentane), 6 yuan of cricoid piperidines (also referred to as azepine hexamethylenes Alkane (azinane)) and the saturated heterocyclics class such as 7 yuan of cricoid hexamethylene imines (also referred to as azepan (azepan)).This Outside, as other examples, are as follows: 1H- ethylene imine, the 2H- ethylene imine of 3 member rings；The azete (azete) of 4 member rings；The pyrroles of 5 member rings (also referred to as azoles (azole))；The pyridine of 6 member rings；Azo-cycle heptantriene (azatropilidene) (also referred to as azepines of 7 member rings (azepine)) compound as reactive group containing 1 or more unsaturated heterocycle class such as.It is not particularly limited, but is preferably saturated miscellaneous 3 yuan of cricoid aziridines of ring.Greatly, nucleophilicity easily occurs for the aziridine weak but steric strain of alkalinity (steric strain) Ring-opening reaction.Therefore, big with the interaction of compound (B), industrially it is also preferred that.
As the concrete example that can be used as 3 yuan of cricoid aziridines that cyclic imines (C1) use, can enumerate with Lower substance.
Monofunctional aliphatic system the aziridine type: for example, aziridine, 1- methylaziridine, 1- ethyl ethylene-imine, 1- third Base ethylene imine, 1- butyl ethylene imine, 1- tert-butyl ethylene imine, 1- hexyl ethylene imine, 1- octyl ethylene imine, 1- decyl ethylene imine, 1- octadecyl ethylene imine, propyleneimine (also referred to as 2- methylaziridine), (S) -2- methylaziridine, 2- ethyl ethylene-imine, 2- propyl ethylene imine, 2- butyl ethylene imine, 2- hexyl ethylene imine, 2- octyl ethylene imine, 2- decyl ethylene imine, 2- octadecyl a word used for translation Third pyridine, 1- hexyl -2- methylaziridine, 2,2- dimethyl ethylene imine, 2,3- dimethyl ethylene imine, 1- (2- ethylbutanoyl base) Ethylene imine, 2- heptyl -3- methylaziridine, -1 Alpha-Methyl ethylene imine of (2R) -1- hexyl, 1,2 α, 3 β-trimethyl ethylene imine, 2, 2,3,3- tetramethyl ethylene imine, -3 Beta-methyl ethylene imine of 2 α-tert-butyl, -1,3 beta-dimethyl ethylene imine of 2 α-isopropyl, 2 α-first - 3 β of base-(1- Methylethyl) ethylene imine, -1,3 beta-dimethyl ethylene imine of 2 α-(tert-butyl), (1S, 2S) -1,2- diisopropyl two Ethylene imine, -3 Beta-methyl ethylene imine of 1,2 α-diisopropyl, two ethylene imine of (1R, 2R) -1,2- diisopropyl, 2 β-(tert-butyl) - - 3 Alpha-Methyl ethylene imine of 1- ethyl, -2 α of 1- isopropyl, 3 alpha-alpha-dimethyl ethylene imines, 1- ethyl -2- methylene ethylene imine, 1- second - 3 β of -2 Alpha-Methyl of base-(1- Methylethyl) ethylene imine, -2 β of 1 β-tert-butyl, 3 beta-dimethyl ethylene imines, 2 α-tert-butyl -1- oneself - 3 β of -3 Beta-methyl ethylene imine of base, -3 β of -2 Alpha-Methyl of 1- ethyl-(1- Methylethyl) ethylene imine and -2 Alpha-Methyl of 1- butyl - (1- Methylethyl) ethylene imine etc..
Monofunctional, aromatic system the aziridine type: for example, 1- phenyl ethylene imine, (R) -2- phenyl ethylene imine, (S) -2- benzene Base ethylene imine, 2- (phenyl methyl) ethylene imine, 2- (phenylethyl) ethylene imine, 2- methyl -2- phenyl ethylene imine, 1- ethyl -2- Phenyl ethylene imine, 1- (phenyl methyl) ethylene imine, (2 β, 3 α) -1,2- dimethyl -3- phenyl ethylene imine, 2- tert-butyl -2- phenyl Ethylene imine, 1- benzyl -2- methylaziridine, 1- benzyl -2- acetyl group -2- methylaziridine, 2- benzyl -3- phenyl ethylene imine, - 2 Alpha-Methyl ethylene imine of (2R) -1- benzyl, (2R, 3R) -1- benzyl -2- phenyl -3- benzoyl ethylene imine, 1- benzyl -2- uncle Butyl-3- methylaziridine, 2-1,3 β of beta-phenyl-dimethyl ethylene imine ,-3 beta-phenyl ethylene imine of 2 Alpha-Methyl, (2S)-2 β-benzene - 3 β of base-benzyl ethylene imine, -2 β of (2R) -1- benzyl, 3 alpha-alpha-dimethyl ethylene imines, 1- (2,4,6- trinitrophenyl) ethylene imine, - 3 β of -2 beta-phenyl of 1- cyclohexyl-(to methoxybenzoyl base) ethylene imine, -2 α of 1- cyclohexyl--3 α of phenyl-are (to methylbenzene first Acyl group) ethylene imine, -3 β of -2 beta-phenyl of 1- cyclooctyl-(to methoxybenzoyl base) ethylene imine, -2 α of 1- cyclooctyl--3 α of phenyl - (to methyl benzoyl) ethylene imine, 1- (2- naphthoyl) ethylene imine, 1- (1,2,3,4- naphthane -2- base) ethylene imine and 1- (p-nitrophenyl formoxyl) ethylene imine etc..
Monofunctional cycloaliphatic system the aziridine type: for example, 1- cyclohexyl ethylene imine, 2- cyclohexyl ethylene imine, 1- (1- gold Rigid alkyl) ethylene imine and 1- (1- norbornane) ethylene imine etc..
Monofunctional vinyl's imines of hydroxyl: for example, 1- (2- hydroxyethyl) aziridine, 2- (ethylene imine -1- Base) -2- propyl alcohol, 3- (2- methylaziridine -1- base) -1,2- propane diol, 1- (heptadecyl carbamoyl) ethylene imine, 1- (dodecylamino formoxyl) aziridine, α-(ethylene imine -1- base) benzyl carbinol, α-(ethylene imine -1- ylmethyl) benzyl Alcohol, α-vinyl-1- ethylene imine ethyl alcohol and α-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-ten seven fluorine nonyl)-1- Ethylene imine ethyl alcohol etc..
The carboxylic the aziridine type or its metal salt of simple function: for example, 1- ethylene imine propane acid, 1- ethylene imine butane Acid, 1- ethylene imine hexane acid, 2- ethylene imine carboxylic acid and 2- ethylene imine carboxylic acid sodium etc..
Monofunctional vinyl's imines containing alkoxy: for example, 1- (methoxy) ethylene imine, 2- (methoxy) a word used for translation Third pyridine, 1- (methoxy ethyl) ethylene imine, 2- (methoxy ethyl) ethylene imine, (2R) -2 Alpha-Methyl -1- (4- methoxy-benzyl) Ethylene imine, 1- (4- methoxy-benzyl) -2- methylaziridine and -2 α of (S)-ethylene imine-carboxylic aldehyde diethyl acetal etc..
Monofunctional vinyl's imines containing ester group: for example, ethylene imine -2- carboxylate methyl ester, 1- ethylene imine carboxylic acid isopropyl, 1- Ethylene imine butyl carboxylate, 1- butyl -2- methylaziridine -2- carboxylate methyl ester, 1- (trityl group) -2- ethylene imine carboxylic acid first Ester, 3- phenyl ethylene imine -2- carboxylic acid, ethyl ester, 1- benzoyl ethylene imine -2- carboxylic acid isopropyl, 1- benzyl -2- methyl a word used for translation third Pyridine -2- carboxylate methyl ester, 1- phenyl -2- methylaziridine -2- carboxylate methyl ester, 1- [(methoxycarbonyl) methoxyl group] ethylene imine -2, 2- dimethyl dicarboxylate, 1- ethylene imine ethyl propionate, 1- ethylene imine propyl propionate, 1- ethylene imine benzyl propionate, 1- ethylene imine third Acid -2- methoxy acrylate, 1- ethylene imine propionic acid -2- propyl ester, 1- ethylene imine isopropyl propionate, 1- ethylene imine propionic acid cyclopropyl first Ester, 1- ethylene imine sec-butyl propionate, 1- ethylene imine propionic acid cycloheptyl ester, 1- ethylene imine cyclohexyl propionate, 1- ethylene imine propionic acid -2- first Base cyclohexyl, 1- ethylene imine propionic acid ring pentyl ester, 1- ethylene imine phenyl propionate, 1- ethylene imine propionic acid peopentyl ester, 1- ethylene imine propionic acid Cinnamic ester, 1- ethylene imine phenylethyl propionate and 1- ethylene imine propionic acid -2- nitro butyl ester etc..
Monofunctional vinyl's imines containing acyl group: for example, 1- acetyl group ethylene imine, 2- acetyl group ethylene imine, 1- butyl- 2- acetyl group -2- methylaziridine, 1- phenyl -2- acetyl group -2- methylaziridine, 1- [(1- naphthoxy) acetyl group] a word used for translation third Pyridine, 1- caproyl ethylene imine, 1- pelargonyl group ethylene imine, 1- lauroyl ethylene imine, 1- oleoyl ethylene imine, 1- stearyl a word used for translation Third pyridine, 1- myristoyl ethylene imine, phenyl (ethylene imine-1- base) ketone, 1- (2- methyl-1-oxopropyl) ethylene imine, 1- (1- oxo butyl) ethylene imine, phenyl (ethylene imine -1- base) ketone and phenyl (ethylene imine -1- base) ketone etc..
Amino-containing monofunctional vinyl's imines: for example, ethylene imine -1- amine, ethylene imine -2- amine, 1- (2- amino-ethyl) Ethylene imine, (2S) -2- [(S) -1- hydroxyethyl] ethylene imine -1- amine, -2 α of (2S)-N- ethyl--3 β of acetyl group-(4- methoxyl group Phenyl) ethylene imine -1- amine, 2- (ethylene imine -1- base) -4,6- dimethoxy -1,3,5- triazine, 6- (ethylene imine -1- base) -1, 3,5- triazine -2,4- diamines and 4,6- bis- (ethylene imine -1- base)-N- (2,2- dimethyl -1,3- dioxanes -5- base) -1,3, 5- triazine -2- amine etc..
Containing aminocarboxy monofunctional vinyl's imines: for example, N- (p-methylphenyl) -1- ethylene imine carboxylic acid amides and N- (4- nitrobenzophenone) -1- ethylene imine carboxylic acid amides etc..
Monofunctional vinyl's imines containing carboxamide groups: for example, N- cyclohexyl-1- ethylene imine carboxylic acid amides, N- methyl-1- Ethylene imine carboxylic acid amides, N, 2- dimethyl -1- ethylene imine carboxylic acid amides, N- benzyl -1- ethylene imine propionamide, N- phenyl ethylene imine -1- Carboxylic acid amides, N- (4- methoxyphenyl) -1- ethylene imine carboxylic acid amides, 1- phenyl -2- methylaziridine -2- carboxylic acid amides, 1- benzyl -2- Methylaziridine -2- carboxylic acid amides, 1- butyl -2- methylaziridine -2- carboxylic acid amides, 1- (2- amino-ethyl) ethylene imine, N- (2- first Phenyl) -1- ethylene imine carboxylic acid amides, N- (1- naphthalene) -1- ethylene imine carboxylic acid amides, N, N- dimethyl -1- ethylene imine carboxylic acyl Amine, N, N- diethyl -1- ethylene imine propionamide and N- (2- methoxyphenyl) -1- ethylene imine carboxylic acid amides etc..
Monofunctional vinyl's imines of nitrile containing carbonyl (carbonitrile) base: for example, 2- ethylene imine carbonyl nitrile, 3- (ethylene imine- 1- yl) propionitrile, 1- phenyl -2- methylaziridine -2- carbonyl nitrile, 1- benzyl -2- methylaziridine -2- carbonyl nitrile, 1- butyl -2- first Base ethylene imine -2- carbonyl nitrile, 1- [(2H3) methyl] ethylene imine -2- carbonyl nitrile, 1- benzoyl ethylene imine -2- carbonyl nitrile, the tertiary fourth oxygen of 1- Base carbonyl ethylene imine -2- carbonyl nitrile and 1- [(p-nitrophenyl oxygroup) acetyl group] ethylene imine etc..
Monofunctional vinyl's imines of cyano-containing: for example, 1- cyano -2,2- dimethyl ethylene imine, 1- (tert-butyl) -2- cyanogen Base -3,3- dipropyl ethylene imine, 1- (tert-butyl) -2- cyano -3,3- diethyl ethylene imine, 1- (tert-butyl) -2- cyano -3- first Base -3- propyl ethylene imine and 1- (tert-butyl) -2- cyano -3,3- dimethyl ethylene imine etc..
Monofunctional vinyl's imines containing sulfonyl: for example, 1- phenyl sulfonyl ethylene imine, 1- [(8- methoxyl group -5- quinoline Quinoline base) sulfonyl] ethylene imine, 4- aminomethyl phenyl (2- butyl ethylene imine -1- base) sulfone, 1- tosyl -2,3- diphenyl a word used for translation Third pyridine, 1- (p-methylphenyl sulfonyl) -2- phenyl ethylene imine and 1- tosyl -2- phenyl -2- tert-butyl ethylene imine etc..
Monofunctional vinyl's imines containing halogen: for example, 1- chlorine ethylene imine, 2- chlorine ethylene imine, the chloro- 2- of (1S, 2S) -1- Methylaziridine, 1- (chlorobenzene formacyl) ethylene imine, α-trichloromethyl -1- ethylene imine methanol, 1- [(4- chlorophenoxy) second Acyl group] ethylene imine, N- (3- chlorphenyl) -1- ethylene imine carboxylic acid amides, 1- [(2- chlorophenoxy) acetyl group] ethylene imine, N- (4- chlorine Phenyl) -1- ethylene imine carboxylic acid amides, N- (3,4- dichlorophenyl) -1- ethylene imine carboxylic acid amides, N- (3,4- dichlorophenyl) -1- a word used for translation third Pyridine propionamide, 2- tert-butyl -2- (methyl fluoride) ethylene imine, seven fluorine butyl ester of 1- ethylene imine propionic acid -2,2,3,3,4,4,4-, 1- a word used for translation Third pyridine propionic acid -2,2,2- trifluoro ethyl ester and 1- tosyl -2- tert-butyl -2- (methyl fluoride) ethylene imine etc..
Monofunctional vinyl's imines containing silicyl: for example, 1- (4- aminomethyl phenyl) -2- trimethoxysilyl a word used for translation Third pyridine, 1- (phenyl) -2- (trimethyl silyl) ethylene imine, 1- (phenyl) -2- (trimethyl silyl) ethylene imine and 1- (phenyl) -2- (trimethyl silyl) ethylene imine etc..
Containing α, β-unsaturated group monofunctional vinyl's imines: for example, 2- methyl (methyl) acrylic acid -2- (ethylene imine -1- Base) ethyl ester, 1- vinyl ethylene imine, β-vinyl -1- ethylene imine ethyl alcohol, β-vinyl -1- ethylene imine alcohol, acetic acid ester, [α S, (-)] -2- methylene-α-vinyl -1- ethylene imine ethyl alcohol, [α R, (+)] -2- methylene-α-vinyl -1- ethylene imine ethyl alcohol, N- allyl -1- ethylene imine propionamide and 1- allyl -3 β--2 α of isopropyl-methylaziridine etc..
2 functional ethylene's imines: for example, 1,1 '-connection ethylene imine, Isosorbide-5-Nitrae-bis- (ethylene imine -1- base) butane, 1,2- ethane The double ethylene imines of glycol bis- (1- ethylene imine propionic esters), bis- (1- the aziridinyl) -1,4- benzoquinones of 3,6-, 1,1 '-terephthaloyl groups, N, N '-ethenylidene bis- (1- ethylene imine carboxylic acid amides), the double ethylene imines of 1,1 '-tetramethylenes bis- (carbonyls), 1,1 '-(eight methylene Dicarbapentaborane) double ethylene imines, the double ethylene imines of 1,1 '-(tetramethylene disulfonyl bases), 1,1 '-(the double sulfonyls of pentamethylene) double a word used for translations Third pyridine, the double ethylene imines of 1,1 '-(eight di-2-ethylhexylphosphine oxide sulfonyls), the double ethylene imines of 1,1 '-(the double sulfonyls of 1,5- naphthylene), 1,1 '- (the double sulfonyls of metaphenylene) double ethylene imines, 1,4- butanediol -1,4- bis- (1- ethylene imine propionic esters), N, N '-diphenylmethyl Alkane -4,4 '-bis- (1- ethylene imine carbonyl compounds), N, N '-Toluene-2,4-diisocyanate, 4- bis- (1- ethylene imine carbonyl compounds), it is double between phenyl-diformyl Base -1- (2- methylaziridine), three -1- aziridinyl phosphine oxides, N, bis- (the 1- ethylene imine carbonylations of N '-hexa-methylene -1,6- Object), diphenyl (bis- -4,4-N of methane -, N '-diethylidene urea), the double-N of diphenyl methane -4,4-, N '-ethylidene-urea, 1,6- Hexamethylene bis-N, N '-ethylidene-urea), bis- [1- (2- ethyl) aziridinyl] benzene -1,3- carboxylic acid amides etc..
3 functional ethylene's imines: for example, three (ethylene imine -2- base) phosphine oxides, the bis- three [3- (1- of hydroxymethyl butanol of 2,2- Aziridinyl) propionic ester], the bis- hydroxymethyl butanol three [3- (2- methyl-1-aziridinyl) propionic ester] of 2,2-, three-2,4,6- (1- aziridinyl) -1,3,5- triazine, 2- methylpentane -2,4- glycol three [3- (1- aziridinyl) propionic ester], 2- methylpent Alkane -2,4- glycol three [3- (1- aziridinyl) butyrate], [3- (1- (2- methyl) ethylene imine of 2- methylpentane -2,4- glycol three Base) propionic ester], 2- methylpentane -2,4- glycol three [3- (1- aziridinyl) -2- methylpropionate] and (Sanya 2,4,6- Ethylimino)-Syn- triazine etc..
4 functional ethylene's imines: for example, [oxygroup is bis-, and (ethyleneoxy group is sub- by 2,4,4,6- tetra- (ethylene imine -1- base) -2,6- Ethyl oxygroup)] -2,4,6- three phospha (V) -1,3,5- triazine and the bis- four [3- (1- of (hydroxymethyl) -1,3- propane diol of 2,2- Aziridinyl) propionic ester] etc..
Furthermore, it is possible to use with intramolecular there is the compound of 1 or more isocyanate group to react by 1- ethylene imine ethyl alcohol Resulting carbamate polyethyleneimine derivative is reacted resulting ester ethylene imine derivative by 1- ethylene imine ethyl alcohol with acid anhydrides or carboxylic acid halides Object etc. has carried out the compound of chemical modification by known reactions.Said derivative can be applied in combination individually or with two or more.
In one embodiment of resin combination of the invention, preferably set by the total amount of ingredient (A), (B) and (C1) When for 100 parts by weight, oligomer (A) is that 1 to 99.8 parts by weight, intramolecular have the α that contains of 1 or more carboxyl, β-unsaturation pair The compound (B) of key base is 0.1 to 49.5 parts by weight and cyclic imines (C1) are the cooperation of 0.1 to 49.5 parts by weight Amount.More preferably (A) is 10 to 80 parts by weight, (B) is 10 to 45 parts by weight and (C1) is the range of 10 to 45 parts by weight.Pass through Make that oligomer (A) is 1 parts by weight or more and (B) and/or (C1) they are 0.1 parts by weight or more, the deficiency of cohesive force can be improved, and It is easy to improve the characteristics such as heat resistance, humidity resistance.On the other hand, by making oligomer (A) to be 99.8 parts by weight or less and (B) And/or (C1) is 49.5 parts by weight hereinafter, when using resin combination as smears or bonding agent, is easy to get excellent To the adaptation or cementability of substrate.
Further, in an embodiment of resin combination of the invention, by the whole of ingredient (B) and ingredient (C1) When weight is set as 100 weight %, the ratio of above-mentioned (C1) is preferably the range of 20 to 80 weight %, more preferably 30 to 70 weights Measure the ratio of %.When making the ratio of above-mentioned (C1) below 80 weight %, be easy inhibit resin combination viscosity rise and Obtain excellent coating.On the other hand, when making the ratio of above-mentioned (C1) more than 20 weight %, resin combination is being used When object is as smears or bonding agent, it is easy to get excellent adaptation or cementability to substrate.
(C2) ingredient:
In the present invention, carbodiimide compound (C2) is that intramolecular has 1 or more carbodiimide key base, i.e.-N=C= Compound of the N- as reactive group.Wherein, preferably intramolecular have 1 to 4 carbodiimide key base compound.In addition, carbon two Imine linkage base can be closed with comprising other key base junctions such as amino, nitro, silicyl, carbonyl, amide groups and ester group.As this hair An example of the manufacturing method of bright middle carbodiimide compound (C2), can enumerate in organic solvent, in the presence of catalyst, will at least Compound with 1 or more isocyanate group carries out the side of carbon dioxide removal reaction under the conditions of 100 to 200 DEG C of temperature Method.When temperature condition is 100 DEG C or less, reaction needs for a long time, on the other hand, then easily occurs at 200 DEG C or more secondary anti- It answers.The reaction preferably carries out in a nitrogen environment.
In the above-mentioned manufacturing method of carbodiimide compound (C2), at least there is 1 or more isocyanic acid as raw material The compound of ester group can be any one of simple function polyisocyanate and polyfunctional isocyanate.It specifically, can be previously to exist Cited various compounds in ingredient (a-2).
As the catalyst candidates used in the reaction for forming carbodiimide key base, can enumerate: phospholene (phospholene) and phospholene oxides (phospholene oxide) class.More specifically, it can be used: 1- ethyl- 3- methyl -3- phospholene oxides, 1- phenyl -3- methyl -3- phospholene oxides and 1- phenyl -3- methyl -3- phospholene Oxide etc..
As the organic solvent used in the reaction for forming carbodiimide key base, it is necessary to which boiling point is high, and not having can With as raw material with the above isocyanate group of at least one compound and carbodiimide compound generated (C2) it is anti- The reactive hydrogen answered.As the concrete example for the organic solvent that can be used in the present invention, following substance can be enumerated.
It is aromatic hydrocarbon: for example, toluene, dimethylbenzene and diethylbenzene etc..
Diol alcohol esters: diethylene glycol diacetate esters, dipropylene glycol dibutyrate, hexylene glycol diacetate esters, glycol diethyl Acid esters, methyl ethyl glycol acetate, glycol acetic acid esters, butyl ethyl glycol acetate, ethyl-two-ethyl glycol acetate and butyl- Two-ethyl glycol acetates etc..
Ketone: ethyl butyl ketone, acetophenone, propionyl benzene, diisobutyl ketone and cyclohexanone etc..
Aliphatic ester: aluminium acetate, propyl propionate, ethyl butyrate etc..
The generation of carbodiimide key base, can be by 2260cm-1Isocyanate group absorption peak disappearance and carbodiimide key base The generation of absorption peak adds their confirmation.
Carbodiimide compound (C2), in addition to above-mentioned basic skills, can also according to such as U.S. Patent No. 2,941, No. 956, Japanese Patent Publication 47-33279 bulletin, Japanese Unexamined Patent Publication 5-178954, Japanese Unexamined Patent Publication 7-330849 bulletin etc. Disclosed method manufactures.In addition, can also be according to J.Org.Chem., 28,2069 (1963), Chem., Review 81, The method manufacture recorded in 619 (1981).In addition, can also be according to recently such as Japanese Unexamined Patent Publication 5-178954 bulletin and Japan It is manufactured as disclosed in Japanese Laid-Open Patent Publication 6-56950 bulletin etc. in the method for solvent-free lower progress.In this specification, by referring to These methods and as part of this specification introduce.
In addition, general, as carbodiimide compound, it is also known that in addition to carbodiimide key base (that is,-N=C=N-) it Outer intramolecular also has the compound of 1 or more isocyanate group.However, the oligomer in the present invention, in resin combination (A) or compound monomer (B) include containing hydroxyl, amino isoreactivity hydrogen functional group when, pass through the isocyanide in above compound Perester radical and above-mentioned functional group reactions, cause dramatically increasing for viscosity.Therefore, use the based resin composition as smears Or when bonding agent, coating is easily made to become difficult.In addition, also easily causing coarse, generation painting trace of coated face etc. no even if can be coated with Good situation, therefore easily reduce adaptation, cementability, it is thus not preferred.Therefore, the carbodiimide chemical combination used in the present invention Object (C2), preferably intramolecular are free of isocyanate group.
It is not particularly limited, the concrete example of workable carbodiimide compound (C2) is as follows in the present invention.
Fatty family carbodiimide class: for example, N, N '-diisopropylcarbodiimide, N, N '-dibutyl carbodiimide, N, N '-di-t-butyl carbodiimide, 1- ethyl -3- tert-butylcarbodiimide etc..
The cyclic carbodimides class such as alicyclic ring or aromatic ring: for example, 1,3- diphenyl carbodiimide, N, N '-di-p-tolyl carbon Diimine, N, N '-bis- (2- aminomethyl phenyl) carbodiimides, N, N '-bis- (2- aminomethyl phenyl) carbodiimides, N, bis- (the 3- first of N '- Base phenyl) carbodiimide, 1- butyl -3- phenyl carbodiimide, bis- (2,3- dipropyl phenyl) carbodiimides, N- ethyl-N ' - Phenyl carbodiimide, bis- (3,4- dipropyl phenyl) carbodiimides, N- phenyl-N '-vinyl carbodiimide, bis- (3,5- dipropyls Base phenyl) carbodiimide, bis- (2,5- dipropyl phenyl) carbodiimides, bis- (2,6- dipropyl phenyl) carbodiimides, bis- (dipropyls Base phenyl) carbodiimide, bis- (dipropyl phenyl) carbodiimides, bis- (2,6- diisopropyl phenyl) carbodiimides, N- benzyl- N '-(1- naphthalene) carbodiimide, N- phenyl-N '-diisopropylcarbodiimide, N, bis- (4- methoxyphenyl) carbodiimides of N '-, N- (2,6- diisopropyl -4- Phenoxyphenyl)-N- tert-butylcarbodiimide, bis- (p-methylphenyl) carbodiimides of 1,3-, N- benzyl Base-N '-(tert-butyl) carbodiimide, N- phenyl-N '-vinyl carbodiimide, N- phenyl-N '-(1- phenyl vinyl) carbon two Imines, N, N '-dicyclohexylcarbodiimide, N- (5,5- dimethyl -3- oxo -1- cyclohexenyl group)-N '-(1- naphthalene) carbon two Imines, N- (5,5- dimethyl -3- oxo -1- cyclohexenyl group)-N '-phenyl carbodiimide, N- (5,5- dimethyl -3- oxo - 1- cyclohexenyl group)-N '-tosyl carbodiimide and N- (5,5- dimethyl -3- oxo -1- cyclohexenyl group)-N '-butyl Carbodiimide etc..
Carbodiimide class with amino or nitro: for example, N- (4- carboxyl -4- aminobutyl) carbodiimide, 1- (3- Dimethylaminopropyl) -3- ethyl carbodiimide, N- propyl-N '-(4- dimethrlaminobutyl) carbodiimide, 3- [(ethyl Carbon imido grpup) amino]-N, N- dimethyl -1- propane amine, N- phenyl-N '-(1,3,5- cycloheptatriene -1- base) carbodiimide, N- Cyclohexyl-N '-(2- morpholinyl ethyl) carbodiimide, N- cyclohexyl-N '-[2- (2- methyl morpholine base) ethyl] carbodiimide, 4- [2- [(cyclohexyl carbon imido grpup) amino] ethyl] -4- methyl morpholine, 1- cyclohexyl -3- (2- morpholinyl ethyl) carbon two The m- p-methyl benzenesulfonic acid ester of imines -, 3- [(ethyl carbon imido grpup) amino]-N, N, N- trimethyl -1- propane aluminium iodide, 1- Ethyl -3- (3- dimethylaminopropyl) carbodiimide, 1- ethyl -3- (3- dimethylaminopropyl) carbodiimide hydrochloride, 1- (3- dimethylaminopropyl) -3- ethyl-carbodiimide hydrochloride, N- (3- dimethylaminopropyl)-N '-ethyl carbon two are sub- Amine hydrochlorate and bis- (4- nitrobenzophenone) carbodiimides of 1,3- etc..
Carbodiimide class containing chlorine: for example, N- ethyl-N '-(3- dimethylaminopropyl) carbodiimide chloride, N, Bis- (the 3- chloro-2-methyl phenyl) carbodiimides of N '-and N- (5,5- dimethyl -3- oxo -1- cyclohexenyl group)-N '-(3- chlorobenzene Base) carbodiimide etc..
Carbodiimide class containing silicyl: for example, bis- (trimethyl silyl) carbodiimides, 1- (triisopropyl first Silylation) -3- (triisopropylsilyl) carbodiimide, 1- (triisopropylsilyl) -3- [bis- (diisopropyl ammonia Base) phosphino-] carbodiimide and 1- (triisopropylsilyl) -3- [bis- (diisopropylaminoethyl) thio phosphino-s] carbodiimide Deng.
In addition, carbodiimide compound (C2) can also be obtained with commodity.For example, as with methyl diphenylene diisocyanate (MDI) it is the single carbon diimine of raw material, can enumerates: Lupranate XTB-3003 (BASF AG's manufacture) and Stabaxol P (manufacture of Sumitomo Byer carbamate company).In addition, as using tetramethyl xylylene diisocyanate as the poly- carbon of raw material Diimine can be enumerated: Carbodilite V-03, V-09 and HMV-8CA (manufacture of Nisshinbo company) etc..These commodity are point With the compound of 1 to 4 carbodiimide key base in sub.These carbodiimide compounds (C2), can be individually or with two or more group It closes and uses.From the perspective of industry, N, N '-diisopropylcarbodiimide and N, N '-dicyclohexyl carbon two are particularly preferably used Imines.
In one embodiment of resin combination of the invention, with the total amount of ingredient (A), (B) and (C2) for 100 weights When measuring part, preferably oligomer (A) be 1 to 99.8 parts by weight, intramolecular there is 1 or more carboxyl contain α, β-unsaturated double-bond base Compound (B) be 0.1 to 49.5 parts by weight and carbodiimide compound (C2) is the use level of 0.1 to 49.5 parts by weight. More preferably (A) is 10 to 80 parts by weight, (B) is 10 to 45 parts by weight and (C2) is the range of 10 to 45 parts by weight.By making Oligomer (A) is 1 parts by weight or more and (B) and/or (C2) are 0.1 parts by weight or more, can improve the deficiency of cohesive force, and hold Easily improve the characteristics such as heat resistance, humidity resistance.On the other hand, by making oligomer (A) to be 99.8 parts by weight or less and (B) And/or (C2) is 49.5 parts by weight hereinafter, using resin combination as smears or bonding agent in use, being easy to get excellent The adaptation or cementability to substrate.
Further, in an embodiment of resin combination of the invention, with the whole of ingredient (B) and ingredient (C2) When weight is 100 weight %, the ratio of above-mentioned (C2) is preferably the range of 20 to 80 weight %, more preferably 30 to 70 weight % Ratio.When making the ratio of above-mentioned (C2) below 80 weight %, it is easy to inhibit the viscosity rising of resin combination to obtain Excellent coating.On the other hand, when making the ratio of above-mentioned (C2) more than 20 weight %, using resin combination as Smears or bonding agent are in use, be easy to get excellent adaptation or cementability to substrate.
In general, above-mentioned (C1) or (C2) containing reactive nitrogen compound, it is known that other than carboxyl, also with ammonia The functional group of the active hydrogen such as base and hydroxyl interacts.But it by the stability of resin combination and is using When resin combination is as smears or bonding agent to the adaptation or cementability of substrate from the perspective of, resin group of the invention It closes object and the nitrogen-atoms of cyclic imide base or carbodiimide key base, the interaction with carboxyl preferably preferentially occurs.Thus viewpoint goes out Hair, ingredient (A) and ingredient (B) are preferably the compound of the not functional group containing reactive hydrogen such as hydroxyl, amino.Therefore, as at Divide (B), it is preferable to use for example: acrylic acid, methacrylic acid, acrylic acid -2- carboxyethyl, single acrylic acid-ω-carboxyl gather in oneself By the obtained end of open loop addition of lactonic ring, with polylactone system (methyl) acrylate of carboxyl, (East Asia synthesizes ester ester etc. Company manufacture, acid esters containing acid propylene " M-5300 ") etc. compounds.
On the other hand, in an embodiment of the invention, mentioned component (C1) or (C2) are preferably intramolecular in addition to ring The compound of other functional groups containing reactive nitrogen such as isocyanate group is free of other than shape imino group or carbodiimide key base.Upper When to state ingredient (C1) or (C2) be the compound containing isocyanate group, compared with the interaction of target, carboxyl is more preferably contributed to Promote to react with moisture, OH base, therefore the bad situations such as blistering that viscosity increases or decarburization acid reaction is caused easily occur.Cause This, bonding agent etc. use on the way, have the tendency that easily cause function reduction.
Described above, resin combination of the invention, it is characterized in that: it include ingredient (A), (B) and (C1) or (C2) conduct Essential component, especially because the interaction of ingredient (B) and ingredient (C1) or (C2), and have and contain α as multifunctional, β-is no It is saturated the performance of the compound of double bond base.Resin combination according to the present invention as a result, with crosslink density improve, it can be achieved that The raising of cohesive force and then the raising of the durabilities such as heat resistance and humidity resistance.Therefore, it in the present invention, is not intended to by making Directly seek the improvement of above-mentioned characteristic with the ingredient other than mentioned component.However, resin combination of the invention, it can be according to it Use form, it is considered desirable to characteristic after, and containing additional ingredient.Hereinafter, being illustrated to an example for the ingredient that can be added.
(D) ingredient:
In one embodiment of resin combination of the invention, resin combination is other than above-mentioned essential component, also Intramolecular can be contained without carboxyl containing α, β-unsaturated double-bond base compound monomer (D).Here, mentioned component (D) is used as Reactive diluent.It in well-known various compounds, can arbitrarily be selected in the art as reactive diluent It selects the not carboxylic compound monomer of intramolecular and uses.That is, mentioned component (D) is free from above-mentioned oligomer (A) and contains carboxylic The compound monomer (B) of base, the reactive compounds monomer distinguished with them.On additional in above-mentioned resin combination It states ingredient (D), the efficient activity and high sensitivity of the copolyreaction of above-mentioned oligomer (A) easy to accomplish and ingredient (B).In addition, can Easily make above-mentioned resin combination lowering viscousity, while being easy to improve workability when coating.It is not particularly limited, as available Make the compound of ingredient (D), compound below can be enumerated.
Aliphatic (methyl) esters of acrylic acid of hydroxyl: more specifically, for example, (methyl) 2-Hydroxy ethyl acrylate [2-Hydroxy ethyl acrylate and the merging of methacrylic acid -2- hydroxy methacrylate are expressed as " (methyl) acrylic acid -2- hydroxyl second Ester ".It is same as below], (methyl) acrylic acid -1- hydroxy propyl ester, (methyl) 2-hydroxypropyl acrylate, (methyl) acrylic acid -3- Hydroxy propyl ester, (methyl) acrylic acid -1- hydroxybutyl, (methyl) acrylic acid -2- hydroxybutyl, (methyl) acrylic acid -3- hydroxyl Butyl ester, (methyl) acrylic acid -4- hydroxybutyl, the own ester of (methyl) acrylic acid -6- hydroxyl, (methyl) acrylic acid -8- hydroxyl monooctyl ester, (methyl) acrylic acid -10- hydroxyl last of the ten Heavenly stems ester, (methyl) acrylic acid -12- hydroxylauric ester, (methyl) acrylic acid ethyl-α-(hydroxyl Methyl) ester, simple function (methyl) glycerol acrylate, (methyl) glycidyl base laurate, (methyl) acrylic acid Glycidyl oleate and (methyl) glycidyl base stearate etc. aliphatic esters system (methyl) acrylate； By polylactone system (methyl) acrylate of the obtained end hydroxyl of the open loop addition of lactonic ring；By ethylene oxide, epoxy Epoxyalkane addition system (methyl) acrylate of the epoxyalkane such as the propane obtained end hydroxyl of addition repeatedly；And (first Base) 2-Hydroxy ethyl acrylate phosphate etc..
Alicyclic ring or aromatic series (methyl) esters of acrylic acid of hydroxyl: for example, (methyl) acrylic acid -1,2- hexamethylene diformazan Alcohol ester, (methyl) acrylic acid -1,3- cyclohexanedimethanoester ester, (methyl) acrylic acid -1,4 cyclohexane dimethanol ester, (methyl) third Olefin(e) acid cyclohexyl glycidyl ether, (methyl) phenylethyl glycidyl ether, (methyl) acrylic acid -2- hydroxyl -3- benzene Oxygroup methyl esters, (methyl) acrylic acid -2- hydroxyl -3- phenoxy ethyl, (methyl) acrylic acid -2- hydroxyl -3- phenoxy-propyl, (methyl) acrylic acid -2- hydroxyl -3- phenoxy group butyl ester, (methyl) acrylic acid -2- hydroxyl -3- phenoxy group last of the ten Heavenly stems ester, (methyl) propylene Acid -2- hydroxyl -3- phenoxy group stearyl, (methyl) acrylic acid monohydroxy ethyl ester phthalic acid ester, (methyl) acrylic acid - 2- (4- benzoyl -3- hydroxyphenoxy) ethyl ester, bis- (2- hydroxypropyl) esters of (methyl) acrylic acid of benzene-two -1,4- and benzene - Bis- (2- hydroxypropyl) esters of two (methyl) acrylic acid -1,3- etc..
Enumerate BTA system (methyl) esters of acrylic acid of hydroxyl: for example, 2- (2 '-hydroxyls -5 '-(methyl) acryloyl-oxy Base ethylphenyl) -2H- benzotriazole is [by 2- (2 '-hydroxyls -5 '-acryloyl-oxyethyl phenyl) -2H- benzotriazole and 2- The merging of (2 '-hydroxyls -5 '-methaciylyloxyethylphenyl) -2H- benzotriazole is expressed as " 2- (2 '-hydroxyls -5 '-(first Base) acryloyl-oxyethyl phenyl) -2H- benzotriazole ".It is same as below], 2- (2 '-hydroxyls -5 '-(methyl) acryloxy Ethylphenyl) the chloro- 2H- benzotriazole of -5-, 2- (2 '-hydroxyls -5 '-(methyl) acryloxypropyl phenyl) -2H- benzo three Azoles, 2- (2 '-hydroxyls -5 '-(methyl) acryloxypropyl phenyl) chloro- 2H- benzotriazole of -5-, 2- (2 '-hydroxyls -3 '-uncle Butyl -5 '-(methyl) acryloyl-oxyethyl phenyl) -2H- benzotriazole and 2- (2 '-hydroxyls -3 '-tert-butyl -5 '-(first Base) acryloyl-oxyethyl phenyl) the chloro- 2H- benzotriazole of -5- etc..
Benzophenone series (methyl) esters of acrylic acid of hydroxyl: for example, 2- hydroxyl -4- { 2- (methyl) acryloxy } Oxethyl-diphenyl-ketone, 2- hydroxyl -4- { 2- (methyl) acryloxy } butoxy benzophenone, 2,2 '-dihydroxy -4- { 2- (methyl) acryloxy } oxethyl-diphenyl-ketone and 2- hydroxyl -4- { 2- (methyl) acryloxy } ethyoxyl -4 '-(2- Hydroxyl-oxethyl) benzophenone etc..
Triazine system (methyl) esters of acrylic acid of hydroxyl: for example, 2,4- diphenyl -6- [2- hydroxyl -4- { 2- (methyl) Acryloyloxyethoxy }]-S- triazine, 2,4- bis- (2- aminomethyl phenyl) -6- [2- hydroxyl -4- { 2- (methyl) acryloxy Ethyoxyl }]-S- triazine, bis- (2- the methoxyphenyl) -6- of 2,4- [2- hydroxyl -4- { 2- (methyl) acryloyloxyethoxy }] - Bis- (2- the ethylphenyl) -6- of S- triazine, 2,4- [2- hydroxyl -4- { 2- (methyl) acryloyloxyethoxy }]-S- triazine, 2,4- Bis- (2- ethoxyl phenenyl) -6- [2- hydroxyl -4- { 2- (methyl) acryloyloxyethoxy }]-S- triazines, the bis- (2,4- bis- of 2,4- Aminomethyl phenyl) -6- [2- hydroxyl -4- { 2- (methyl) acryloyloxyethoxy }]-S- triazine, bis- (the 2,4- diethoxies of 2,4- Phenyl) -6- [2- hydroxyl -4- { 2- (methyl) acryloyloxyethoxy }]-S- triazine and bis- (the 2,4- diethylbenzenes of 2,4- Base) -6- [2- hydroxyl -4- { 2- (methyl) acryloyloxyethoxy }]-S- triazine etc..
α with multiple hydroxyls, β-unsaturated compound class: for example, propylene glycol, butylene glycol, heptene glycol, octene Glycol, two (methyl) glycerol acrylates and adjacent two (methyl) allyl bisphenol-As etc..
(methyl) acrylic amide of hydroxyl: for example, N- hydroxyethyl (methyl) acrylamide is [by N- hydroxyethyl third Acrylamide and the merging of N- hydroxyethyl methacrylamide are expressed as " N- hydroxyethyl (methyl) acrylamide ".It is same as below], N- hydroxypropyl (methyl) acrylamide, N- hydroxybutyl (methyl) acrylamide, N- hydroxyl hexyl (methyl) acrylamide, And N- hydroxy octyl (methyl) acrylamide etc..
(methyl) alkyl-acrylates: for example, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) third Olefin(e) acid -1- propyl ester, (methyl) acrylic acid -2- propyl ester, (methyl) n-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) Isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) acrylic acid n-pentyl ester, (methyl) isoamyl acrylate, (methyl) The just own ester of acrylic acid, (methyl) acrylic acid-2-ethyl caproite, (methyl) n-octyl, (methyl) Isooctyl acrylate monomer, The positive nonyl ester of (methyl) acrylic acid, the different nonyl ester of (methyl) acrylic acid, (methyl) decyl acrylate, (methyl) lauryl ester, (methyl) octadecyl acrylate, (methyl) lauryl acrylate and (methyl) stearyl acrylate etc..
(methyl) acrylic acid ring-type esters: for example, (methyl) cyclohexyl acrylate, (methyl) acrylic acid-1- methyl-1-ring Pentyl ester, (methyl) acrylic acid -1- ethyl -1- ring pentyl ester, (methyl) acrylic acid -1- isopropyl -1- ring pentyl ester, (methyl) propylene Acid-1- methyl-1-cyclohexyl, (methyl) acrylic acid-1- ethyl-1- cyclohexyl, (methyl) acrylic acid-1- isopropyl-1- hexamethylene Ester, (methyl) acrylic acid -1- ethyl -1- ring monooctyl ester, (methyl) benzyl acrylate, (methyl) isobornyl acrylate, (methyl) Phenyl acrylate, (methyl) acrylic acid -2- phenoxy ethyl, (methyl) acrylic acid -2- oxo -1,2- phenyl chlorocarbonate, (methyl) Acrylic acid -2- oxo -1,2- diphenyl ethyl ester, (methyl) acrylic acid -1- naphthalene ester, (methyl) acrylic acid -2- naphthalene ester, (methyl) Acrylic acid -1- naphthalene methyl esters, (methyl) acrylic acid -1- anthracene ester, (methyl) acrylic acid -2- anthracene ester, (methyl) acrylic acid -9- anthracene Ester, (methyl) acrylic acid -9- anthrylmethyl, (methyl) acrylic acid -2- methyl adamantane base -2- ester, (methyl) acrylic acid -2- second Adamantyl -2- ester, (methyl) acrylic acid -2- n-propyl adamantyl -2- ester, (methyl) acrylic acid -2- isopropyl Buddha's warrior attendant Alkyl -2- ester, (methyl) acrylic acid -1- (adamantane -1- base) -1- Methylethyl, (methyl) acrylic acid -1- (adamantane -1- Base) -1- diethyl acetamidomalonate, (methyl) acrylic acid -1- (adamantane -1- base) -1- methyl propyl ester, (methyl) acrylic acid -1- (Buddha's warrior attendant Alkane -1- base) -1- ethylpropyl, (methyl) acrylic acid -5- oxo -4- oxa--tricyclic [4.2.1.03,7] nonyl- 2- base ester, (first Base) acrylic acid -5- oxo -4- oxa--tricyclic [5.2.1.03,8] decyl- 2- base ester, (methyl) propylene acid dihydride-α-pine tar ester (dihydro- α-terpinyl (meth) acrylate), (methyl) acrylic acid -6- oxo -7- oxa--bicyclic [3.2.1] octyl- 2- base ester and (methyl) acrylic acid -7- oxo -8- oxa--bicyclic [3.3.1] octyl- 2- base ester etc..
Fatty family (methyl) esters of acrylic acid with 1 carbonyl: for example, (methyl) acrylic acid (methoxycarbonyl) first Ester, (methyl) acrylic acid (methoxycarbonyl) ethyl ester, (methyl) acrylic acid (methoxycarbonyl) propyl ester, (methyl) acrylic acid (first Epoxide carbonyl) butyl ester, (methyl) acrylic acid (methoxycarbonyl) last of the ten Heavenly stems ester, (methyl) acrylic acid (ethoxy carbonyl) methyl esters, (first Base) acrylic acid (ethoxy carbonyl) ethyl ester, (methyl) acrylic acid (ethoxy carbonyl) propyl ester, (methyl) acrylic acid (ethyoxyl carbonyl Base) butyl ester, the own ester of (methyl) acrylic acid (ethoxy carbonyl), (methyl) acrylic acid (ethoxy carbonyl) monooctyl ester, (methyl) propylene Acid -2- (ethyoxyl carbonyloxy group) ethyl ester, (methyl) acrylic acid -2- (ethyoxyl carbonyloxy group) propyl ester, (methyl) acrylic acid -2- (second Oxygroup carbonyloxy group) butyl ester, the own ester of (methyl) acrylic acid -2- (ethyoxyl carbonyloxy group), (methyl) acrylic acid -2- (ethyoxyl carbonyl oxygen Base) monooctyl ester, (methyl) acrylic acid -2- (propoxyl group carbonyloxy group) ethyl ester, (methyl) acrylic acid -2- (butoxy carbonyl oxy) ethyl ester, (methyl) acrylic acid -2- (butoxy carbonyl oxy) butyl ester, (methyl) acrylic acid -2- (octyloxy carbonyloxy group) ethyl ester and (methyl) Acrylic acid -2- (octyloxy carbonyloxy group) butyl ester etc..
Fatty family (methyl) esters of acrylic acid with 2 carbonyls: for example, (methyl) acrylic acid -2- oxobutanoyl Ethyl ester, (methyl) acrylic acid -2- oxobutanoyl propyl ester, (methyl) acrylic acid -2- oxobutanoyl butyl ester, (methyl) propylene The own ester of acid -2- oxobutanoyl, (methyl) acrylic acid -2- oxobutanoyl monooctyl ester, (methyl) acrylic acid -2- oxobutanoyl Last of the ten Heavenly stems ester, (methyl) acrylic acid -2- oxobutanoyl dodecane ester, (methyl) acrylic acid -3- oxobutanoyl ethyl ester, (methyl) third Olefin(e) acid -3- oxobutanoyl propyl ester, (methyl) acrylic acid -3- oxobutanoyl butyl ester, (methyl) acrylic acid -3- oxobutanoyl Own ester, (methyl) acrylic acid -3- oxobutanoyl monooctyl ester, (methyl) acrylic acid -3- oxobutanoyl last of the ten Heavenly stems ester, (methyl) propylene Acid -3- oxobutanoyl dodecane ester, (methyl) acrylic acid -4- cyano oxobutanoyl ethyl ester, (methyl) acrylic acid -4- cyanogen Base oxobutanoyl propyl ester, (methyl) acrylic acid -4- cyano oxobutanoyl butyl ester, (methyl) acrylic acid -4- cyano oxo fourth The own ester of acyl group, (methyl) acrylic acid -4- cyano oxobutanoyl monooctyl ester, two (oxobutanoyls) third of (methyl) acrylic acid -2,3- Ester, (methyl) acrylic acid -2,3- two (oxobutanoyl) butyl ester, the own ester of (methyl) acrylic acid -2,3- two (oxobutanoyl), And (methyl) acrylic acid -2,3- two (oxobutanoyl) monooctyl ester etc..
(methyl) acrylic acid ring-type esters with carbonyl: for example, (methyl) acrylic acid -9- methoxycarbonyl -5- oxygen Generation -4- oxa--tricyclic [4.2.1.03,7] nonyl- 2- base ester, (methyl) acrylic acid -10- methoxycarbonyl -5- oxo -4- oxygen Miscellaneous-tricyclic [5.2.1.03,8] nonyl- 2- base ester, (methyl) acrylic acid -4- methoxycarbonyl -6- oxo -7- oxa--bicyclic [3.2.1] octyl- 2- base ester and (methyl) acrylic acid -4- methoxycarbonyl -7- oxo -8- oxa--bicyclic [3.3.1] octyl- 2- Base ester etc..
(methyl) acrylic amide with carbonyl: for example, N- (2- oxobutanoyl ethyl) (methyl) acrylamide, N- (2- oxobutanoyl propyl) (methyl) acrylamide, N- (2- oxobutanoyl butyl) (methyl) acrylamide, N- (2- oxo Bytyry hexyl) (methyl) acrylamide, N- (2- oxobutanoyl octyl) (methyl) acrylamide and diacetone (methyl) third Acrylamide etc..
Further (methyl) esters of acrylic acid containing unsaturated group: for example, (methyl) acrylic acid (methyl) allyl ester, (first Base) acrylic acid -1- butene esters, (methyl) acrylic acid -2- butene esters, (methyl) acrylic acid -3- butene esters, (methyl) acrylic acid - 1,3- methyl -3- butene esters, (methyl) acrylic acid -2- chlorine-2-propylene, (methyl) acrylic acid -3- chlorine-2-propylene, (first Base) the o- 2- acrylic phenyl ester of acrylic acid -, (methyl) acrylic acid -2- (2- propenyloxy group) ethyl ester, (methyl) acrylic acid -2- propylene Base lactate, (methyl) acrylic acid -3,7- dimethyl oct-6-ene -1- base ester, (methyl) acrylic acid rose ester (rhodinyl (meth) acrylate), (methyl) acrylic acid cinnamic ester and (methyl) vinyl acrylate etc..
(methyl) perfluoroethyl alkyl ester class: for example, (methyl) perfluoroethyl methyl esters, (methyl) perfluoroethyl second Ester, (methyl) perfluoroethyl propyl ester, (methyl) perfluoroethyl butyl ester, (methyl) perfluoroethyl monooctyl ester, (methyl) propylene Sour trifluoromethyl methyl esters, (methyl) acrylic acid -2- trifluoromethyl ethyl ester, two perfluoro-methyl methyl esters of (methyl) acrylic acid, (methyl) Acrylic acid -2- perfluoro-ethyl ethyl ester, (methyl) acrylic acid -2- perfluoro-methyl -2- perfluoro-ethyl methyl esters, (methyl) acrylic acid three Perfluoro-methyl methyl esters, (methyl) acrylic acid -2- perfluoro-ethyl -2- perfluoro butyl ethyl ester, (methyl) acrylic acid -2- perfluoro hexyl Ethyl ester, (methyl) acrylonitrile-acrylic acid -2- perfluoro decyl ethyl ester and (methyl) acrylic acid -2- perfluor cetyl ethyl ester etc..
Amino-containing (methyl) esters of acrylic acid: for example, (methyl) acrylic acid-N- methylamino ethyl ester, (methyl) propylene Acid-N- tributyl amino ethyl ester, (methyl) acrylic acid-N, N- dimethylamino ethyl ester, (methyl) acrylic acid-N, N- diethyl Amino ethyl ester, (methyl) acrylic acid-N, N- diethylamino methyl esters, (methyl) acrylic acid pentamethvl ester, (methyl) propylene Acrylic acid tetramethyl piperidine ester and 2,4- diamino -6,2- methacryloxyethyl-s- triazine etc..
(methyl) esters of acrylic acid containing oxygen-containing atom heterocycle: for example, (methyl) glycidyl acrylate, (first Base) acrylic acid (3,4- epoxycyclohexyl) methyl esters, (methyl) acrylic acid (3- methyl -3- oxetanylmethoxy) methyl esters, (methyl) third Olefin(e) acid tetrahydrochysene chaff ester, (methyl) acrylic acid -2- oxo tetrahydropyran -4-base ester, (methyl) acrylic acid -4- methyl -2- oxo four Hydrogen pyrans -4- base ester, (methyl) acrylic acid -4- ethyl-2-oxo tetrahydropyran -4-base ester, (methyl) acrylic acid -4- propyl - 2- oxo tetrahydropyran -4-base ester, (methyl) acrylic acid -5- oxo-tetrahydrofuran -3- base ester, (methyl) acrylic acid -2,2- two Methyl -5- oxo-tetrahydrofuran -3- base ester, (methyl) acrylic acid -4,4- dimethyl -5- oxo-tetrahydrofuran -3- base ester, (first Base) acrylic acid -2- oxo-tetrahydrofuran -3- base ester, (methyl) acrylic acid -4,4- dimethyl -2- oxo-tetrahydrofuran -3- base Ester, (methyl) acrylic acid -5,5- dimethyl -2- oxo-tetrahydrofuran -3- base ester, (methyl) acrylic acid -2- oxo-tetrahydrofuran - 3- base ester, (methyl) acrylic acid -5- oxo-tetrahydrofuran -2- base methyl esters, (methyl) acrylic acid -3,3- dimethyl -5- oxo four Hydrogen furans -2- base methyl esters and (methyl) acrylic acid -4,4- dimethyl -5- oxo-tetrahydrofuran -2- base methyl esters etc..
(methyl) esters of acrylic acid containing alkoxysilyl: for example, 3- (methyl) acryloxypropyl two Methoxy silane, 3- (methyl) acryloyloxypropyltrimethoxysilane, 3- (methyl) acryloxypropyl tripropoxy Silane, three butoxy silane of 3- (methyl) acryloxypropyl, 3- (methyl) acryloxypropyl dimethoxy silicon Alkane, 3- (methyl) acryloyloxy propyl methyl diethoxysilane, 3- (methyl) acryloxypropyl ethyl dimethoxy Silane, 3- (methyl) acryloxypropyl butyldimethoxysilane, 3- (methyl) acryloxypropyl ethyl dipropyl oxygen Base silane, 3- (methyl) acryloyloxy propyl methyl diethoxysilane, 3- (methyl) acryloxypropyl trimethoxy Silane, 3- (methyl) acryloxypropyl triethoxysilane and 3- (methyl) acryloxypropyl tripropoxy silane Deng.
(methyl) alkyl-acrylates containing sulfonyl: for example, (methyl) sulfoethyl methyl esters, (methyl) propylene Acid -2- Sulfoethyl esters, (methyl) acrylic acid -2- sulphopropyl, (methyl) acrylic acid -3- sulphopropyl, (methyl) acrylic acid -2- Sulfo group butyl ester, (methyl) acrylic acid -4- sulfo group butyl ester, (methyl) acrylic acid -2- sulfo group butyl ester, (methyl) acrylic acid -6- sulfo group Own ester, (methyl) sulfoethyl monooctyl ester, (methyl) sulfoethyl last of the ten Heavenly stems ester, (methyl) sulfoethyl lauryl and (first Base) sulfoethyl stearyl ester etc..
(methyl) acrylic acid ring-type esters containing sulfonyl: for example, (methyl) sulfoethyl phenoxy ethyl, (first Base) sulfoethyl cyclohexyl and (methyl) sulfoethyl benzyl ester etc..
(methyl) esters of acrylic acid containing phosphonic acid base: for example, (methyl) acrylic acid acid phosphinylidyne oxygroup ethyl ester, (methyl) third Olefin(e) acid acid phosphinylidyne oxygroup propyl ester, (methyl) acrylic acid acid phosphinylidyne oxygroup butyl ester, the chloro- 2- acid phosphorus of (methyl) acrylic acid -3- The chloro- 2- acid phosphinylidyne oxygroup propyl ester of acyloxy ethyl ester, (methyl) acrylic acid -3-, the chloro- 2- acid phosphinylidyne of (methyl) acrylic acid -3- Oxygroup butyl ester, phosphoric acid phenyl -2- (methyl) acryloyloxyethyl ester, (methyl) acrylic acid acid phosphinylidyne oxygroup ethylene oxide (ring Oxidative ethane addition molal quantity 4 to 10) and (methyl) acrylic acid acid phosphinylidyne oxygroup propylene oxide (propylene oxide addition molal quantity 4 10) etc. to.
(methyl) esters of acrylic acid containing alkoxy: for example, (methyl) acrylic acid -2- methoxy acrylate, (methyl) propylene Acid -2- ethoxy ethyl ester, (methyl) acrylic acid -2- propoxy ethyl, (methyl) acrylic acid -3- propoxy ethyl, (methyl) third Olefin(e) acid -2- butoxyethyl, (methyl) acrylic acid -3- butoxyethyl and (methyl) acrylic acid -4- butoxyethyl etc..
(methyl) acrylic acid derivative class containing epoxyalkane: for example, the alkylene oxide adducts etc. of (methyl) acrylic acid.
2 functions (methyl) esters of acrylic acid: for example, two (methyl) acrylic acid epoxy ethane, two (methyl) acrylic acid tricyclics Oxidative ethane, two (methyl) acrylic acid tetraoxanes, two (methyl) acrylic acid polyethylene oxide, two (methyl) acrylic acid epoxies third Alkane, two (methyl) acrylic acid diepoxy propane, two (methyl) acrylic acid, three propylene oxide, two (methyl) acrylic acid polycyclic oxygen third Alkane, two (methyl) acrylic acid epoxy butane, two (methyl) acrylic acid epoxy pentanes, two (methyl) acrylic acid -2,2- dimethyl propylenes Ester, two (methyl) dihydroxypropyl valeryl hydroxy new pentane acid esters (being commonly referred to as MANDA), two (methyl) dihydroxypropyls new penta Two caprolactone of acyl group hydroxy new pentane acid ester, two (methyl) acrylic acid -1,6- hexane diol esters, two (methyl) acrylic acid -1,2- oneself Alkane diol ester, two (methyl) acrylic acid -1,5- hexane diol esters, two (methyl) acrylic acid -2,5- hexane diol esters, two (first Base) acrylic acid -1,7- heptane diol ester, two (methyl) acrylic acid -1,8- octane diol esters, two (methyl) acrylic acid -1,2- are pungent Alkane diol ester, two (methyl) acrylic acid -1,9- nonane diol esters, two (methyl) acrylic acid -1,2- decanediol esters, two (methyl) Acrylic acid -1,10- decanediol ester, two (methyl) acrylic acid -1,2- decanediol esters, two (methyl) acrylic acid -1,12- ten Dioxane diol ester, two (methyl) acrylic acid -1,2- dodecanediol esters, two (methyl) acrylic acid -1,14- tetradecane diols esters, Two (methyl) acrylic acid -1,2- tetradecane diols esters, two (methyl) acrylic acid -1,16- hexadecane diol esters, two (methyl) propylene Acid -1,2- hexadecane diol ester, two (methyl) acrylic acid -2- methyl -2,4- pentane diol esters, two (methyl) acrylic acid -3- first Base -1,5- pentane diol ester, two (methyl) acrylic acid -2- methyl -2- propyl -1,3- propane diol esters, two (methyl) propylene Acid -2,4- dimethyl -2,4- pentane diol ester, two (methyl) acrylic acid -2,2- diethyl -1,3- propane diol esters, two (first Base) acrylic acid -2,2,4- trimethyl -1,3- pentane diol ester, two (methyl) acrylic acid dihydroxymethyl octane esters, two (methyl) third Olefin(e) acid -2- ethyl -1,3- hexane diol ester, two (methyl) acrylic acid -2,5- dimethyl -2,5- hexane diol esters, two (methyl) Acrylic acid -2- methyl-1,8- octane diol ester, two (methyl) acrylic acid -2- butyl -2- ethyl -1,3- propane diol esters, two (methyl) acrylic acid -2,4- diethyl -1,5- pentane diol ester, two (methyl) acrylic acid -1,2- hexane diol esters, two (first Base) acrylic acid -1,5- hexane diol ester, two (methyl) acrylic acid -2,5- hexane diol esters, two (methyl) acrylic acid -1,7- heptan Alkane diol ester, two (methyl) acrylic acid -1,8- octane diol esters, two (methyl) acrylic acid -1,2- octane diol esters, two (methyl) Acrylic acid -1,9- nonane diol ester, two (methyl) acrylic acid -1,2- decanediol esters, two (methyl) acrylic acid -1,10- decane Diol ester, two (methyl) acrylic acid -1,2- decanediol esters, two (methyl) acrylic acid -1,12- dodecanediol esters, two (first Base) acrylic acid -1,2- dodecanediol ester, two (methyl) acrylic acid -1,14- tetradecane diols esters, two (methyl) acrylic acid -1, 2- tetradecane diols ester, two (methyl) acrylic acid -1,16- hexadecane diol esters, two (methyl) acrylic acid -1,2- hexadecane diols Ester, two (methyl) acrylic acid -2- methyl -2,4- pentane esters, two (methyl) acrylic acid -3- methyl-1s, 5- pentane diol ester, two (methyl) acrylic acid -2- methyl-2-propyl -1,3- propane diol ester, two (methyl) acrylic acid -2,4- dimethyl -2,4- pentanes Diol ester, two (methyl) acrylic acid -2,2- diethyl -1,3- propane diol esters, two (methyl) acrylic acid -2,2,4- trimethyls - 1,3- pentane diol ester, two (methyl) acrylic acid dihydroxymethyl octane esters, two (methyl) acrylic acid-2-ethyl -1,3- hexanes two Alcohol ester, two (methyl) acrylic acid -2,5- dimethyl -2,5- hexane diol esters, two (methyl) acrylic acid -2- butyl -2- ethyls - 1,3- propane diol ester, two (methyl) acrylic acid -2,4- diethyl -1,5- pentane diol esters, two (methyl) acrylic acid -1,2- gold Rigid alkane diol ester, two (methyl) acrylic acid -1,3- adamantane diol esters, two (methyl) acrylic acid -1,4- adamantane diol esters, two (methyl) acrylic acid tricyclodecyl dihydroxy methyl esters, two (methyl) acrylic acid -1,1,1- trihydroxy methyl ethane esters, two (methyl) third Olefin(e) acid tristane dihydroxy methyl esters, two (methyl) acrylic acid tristane dihydroxy methyl esters, two caprolactone, two (methyl) propylene The tetraoxane addition product of bis- (hydroxy phenyl) the propane esters of acid -2,2-, bis- (hydroxy phenyl) first of two (methyl) acrylic acid -2,2- The tetraoxane addition product of alkyl ester, two (methyl) acrylic acid -4,4 '-sulfonyldiphenol esters tetraoxane addition product, Tetraoxane addition product, two (methyl) acrylic acid-of bis- (hydroxy phenyl) the propane esters of two (methyl) acrylic acid-hydrogenation -2,2- Tetraoxane addition product, two (methyl) acrylic acid-bis- (hydroxyls of hydrogenation -2,2- of bis- (hydroxy phenyl) the methane esters of hydrogenation -2,2- Phenyl) propane ester, bis- (hydroxy phenyl) the methane esters of two (2- methyl) propionic acid-hydrogenation -2,2-, -2,2- pairs, two (methyl) acrylic acid - two caprolactone of tetraoxane addition product of (hydroxy phenyl) propane ester and two (methyl) acrylic acid -2,2- are bis- (hydroxy phenyl) - two caprolactone of tetraoxane addition product of methane ester etc..
3 functions (methyl) esters of acrylic acid: for example, three (methyl) acrylic acid -1,2, three alcohol ester of 3- propane, three (methyl) third Olefin(e) acid -2- methylpentane -2,4- diol ester, three (methyl) acrylic acid -2- methylpentane -2,4- diol esters, three caprolactone, three (first Base) acrylic acid -2,2- dimethylpropane -1,3- diol ester, three (methyl) acrylic acid Trimethylolhexane esters, three (methyl) propylene Sour trihydroxy methyl octane ester, bis- (the hydroxymethyl) -1,3- propane diol esters of three (methyl) acrylic acid -2,2-, three (methyl) propylene Acid -1,1,1- trihydroxy methyl ethane ester, three (methyl) acrylic acid -1,1,1- trihydroxy methyl propane esters, three (methyl) propylene Modified three-(2- acryloyl-oxyethyl) isocyanuric acid esters of sour ethoxylation isocyanuric acid, 6-caprolactone and three (methyl) propylene Sour pentaerythritol ester etc..
Multifunctional (methyl) acrylate class: for example, four (methyl) acrylate, pentaerythritols, four (methyl) acrylic acid Ethoxylation pentaerythritol ester, four two-trihydroxymethylpropanyl esters of (methyl) acrylic acid, six (methyl) acrylic acid dipentaerythritols Ester, bis- (the hydroxymethyl) -1,3- propane diol esters of four (methyl) acrylic acid -2,2-, the four bis- (hydroxyls of (methyl) acrylic acid -2,2- Methyl) four caprolactone of -1,3- propane diol ester, four two -1,2,3- propane of (methyl) acrylic acid, three alcohol ester, four (methyl) propylene Sour two -2- methylpentane -2,4- diol esters, four (methyl) acrylic acid, two -2- methylpentane -2,4- diol ester, four caprolactone, four Two -2,2- dimethyl pentane -1,3- diol ester of (methyl) acrylic acid, four (methyl) two-tri hydroxy methyl butane of acrylic acid esters, four (methyl) two-Trimethylolhexane of acrylic acid ester, four (methyl) acrylic acid two-trihydroxy methyl octane esters, four (methyl) acrylic acid Bis- (the hydroxymethyl) -1,3- propane diol esters of two -2,2-, six bis- (the hydroxymethyl) -1,3- third of two -2,2- of (methyl) acrylic acid Alkane diol ester, bis- (the hydroxymethyl) -1,3- propane diol esters of six three -2,2- of (methyl) acrylic acid, seven (methyl) acrylic acid three - Bis- (the hydroxymethyl) -1,3- propane diol esters of 2,2-, eight bis- (the hydroxymethyl) -1,3- propane two of three -2,2- of (methyl) acrylic acid Alcohol ester and bis- (the hydroxymethyl) -1,3- propane diol esters of two -2,2- of polyalkylene oxide seven (methyl) acrylic acid etc..
Ethylene unsaturated monomer class containing alkoxysilyl: for example, (methyl) allyl chlorosilane, (methyl) Allyltrimethoxysilanis, (methyl) allyltriethoxysilane, (methyl) allyl amino trimethyl silane, diethoxy Base ethylethylene base silane, trichloro ethylene base silane, trimethoxyvinyl silane, Triethoxyvinylsilane, 3 third oxygen Base vinyl silanes and vinyl three (2- methoxy ethoxy) silane etc..
Aromatic vinyl base system monomer class: for example, styrene, α-methylstyrene, 2-methyl styrene, 3- methylbenzene Ethylene, 4- methyl styrene, 2- methoxy styrene, 3- methoxy styrene, 4- methoxy styrene, 4- tert-butoxy benzene second Alkene, 4- tert-butoxy-α-methylstyrene, 4- (2- ethyl -2- propoxyl group) styrene, 4- (2- ethyl -2- propoxyl group)-α - Methyl styrene, 4- (1- ethoxy ethoxy) styrene, 4- (1- ethoxy ethoxy)-α-methylstyrene, 1- butyl benzene Ethylene and the chloro- 4- isopropenylbenzene of 1- etc..
Fatty family or aromatic system (methyl) acrylic amide: for example, (methyl) acrylamide, N- methyl (methyl) third Acrylamide, N- ethyl (methyl) acrylamide, N- propyl (methyl) acrylamide, N- isopropyl (methyl) acrylamide, N- fourth Base (methyl) acrylamide, N- propyl (methyl) acrylamide, N- tert-butyl (methyl) acrylamide, N- hexyl (methyl) propylene Amide, N- octyl (methyl) acrylamide, N- nonyl (methyl) acrylamide, N- tricosyl (methyl) acrylamide, N- Nonadecyl (methyl) acrylamide, N- docosyl (methyl) acrylamide, N- methylene (methyl) acrylamide, N- ten Trialkyl (methyl) acrylamide, N- (4- Carbamoylphenyl) (methyl) acrylamide, β-(2- furyl) (methyl) third Bis- (2- furyl) acrylamides of acrylamide, 2,3-, N- (9H- fluorenes -2- base) (methyl) acrylamide, 2,3,3- trichlorine (first Base) acrylamide, N- [(R) -1- phenylethyl] (methyl) acrylamide, N- [(S) -1- phenylethyl] (methyl) acryloyl Amine, N- (5,5- dimethylhexanyl) (methyl) acrylamide, (Z)-N- methyl -3- (phenyl) (methyl) acrylamide, (Z) - 3- (phenyl) (methyl) acrylamide, N, N- diethyl -3- phenyl (methyl) acrylamide, N- [2- (1H- imidazoles -5- base) second Base] (methyl) acrylamide, (Z)-N, N- dimethyl -3- (phenyl) (methyl) acrylamide, crotonamide, maleic amide, richness Horse amide, mesaconoyl amine, citraconoyl amine, clothing health amide, 3- phenyl -2- acrylamide, 2- methyl propyl- 2- acrylamide, N, N- bis- Methyl (methyl) acrylamide, N, N- diethyl (methyl) acrylamide, N- [3- (N ', N '-dimethyl amino) propyl]-(first Base) acrylamide, N- (dibutylaminomethyl) (methyl) acrylamide, N- Methyl-N-phenyl (methyl) acrylamide, N- second Alkenyl methane amide and N- vinyl acetamide etc..
(methyl) acrylic amide of the alkoxy containing N-: for example, N- methoxy (methyl) acrylamide, N- methoxy Base ethyl (methyl) acrylamide, N- methoxy-propyl (methyl) acrylamide, N- methoxybutyl (methyl) acrylamide, N- methoxyethyl (methyl) acrylamide, N- methoxyoctyl (methyl) acrylamide, N- methoxyl group decyl (methyl) propylene Amide, N- methoxyl group dodecyl (methyl) acrylamide, N- methoxyl group octadecyl (methyl) acrylamide, N- (ethoxymethyl) Base (methyl) acrylamide, N- ethoxyethyl group (methyl) acrylamide, N- ethoxycarbonyl propyl (methyl) acrylamide, N- second Oxygroup butyl (methyl) acrylamide, N- ethoxyhexyl (methyl) acrylamide, N- ethyoxyl octyl (methyl) acryloyl Amine, N- i-propoxymethyl (methyl) acrylamide, N- isopropoxyethyl (methyl) acrylamide, N- isopropoxide propyl (methyl) acrylamide, N- isopropoxy butyl (methyl) acrylamide, N- isopropoxy hexyl (methyl) acrylamide, N- Isopropoxy octyl (methyl) acrylamide, N- butoxymethyl (methyl) acrylamide, N- butoxyethyl group (methyl) propylene Amide, N- butoxypropyl (methyl) acrylamide, N- butoxybutyl (methyl) acrylamide, N- butoxy hexyl (first Base) acrylamide, N- butoxy octyl (methyl) acrylamide, N- isobutoxymethyl (methyl) acrylamide, N- isobutyl oxygen Base ethyl (methyl) acrylamide, N- isobutoxy propyl (methyl) acrylamide, N- isobutoxy butyl (methyl) acryloyl Amine, N- isobutoxy hexyl (methyl) acrylamide, N- isobutoxy octyl (methyl) acrylamide, N- (amoxy methyl) (methyl) acrylamide, N-1- methyl -2- methoxy ethyl (methyl) acrylamide, N- (oxetanes -2- ylmethoxy Methyl) (methyl) acrylamide, N- (oxetanes -3- ylmethoxymethyl) (methyl) acrylamide, N, bis- (methoxy of N- Ylmethyl) (methyl) acrylamide and N, N- bis- (ethoxyl methyl) (methyl) acrylamide etc..
(methyl) acrylic amide containing sulfonic acid: for example, (methyl) acrylamide sulfonic acid, tert-butyl-(methyl) acryloyl Amine sulfonic acid and (methyl) acrylamide-2- methyl-1-propane sulfonic acid etc..
(methyl) acrylic amide of the base containing cyclic amide: for example, 4- acryloyl morpholine, N- vinyl -2- pyrrolidines Ketone and N- vinyl-Epsilon-caprolactam etc..
The ethylene unsaturated monomer class of nitrile group-containing: for example, (methyl) acrylonitrile, α-chloro-acrylonitrile, crotonic nitrile, Malaysia Nitrile, flumaronitrile, middle health nitrile, lemon health nitrile, clothing health nitrile and (methyl) 2-cyanoethyl acrylate etc..
The heterocyclic vinyl base system monomer class of nitrogen atom: for example, 2- vinylpyridine, 4-vinylpridine, 2- vinyl Piperazine, N- vinyl imidazole, 4- vinyl piperazine and 2,4- diamino -6- vinyl-s- triazine etc..
Maleimide derivatives class: for example, maleimide, methylmaleimido, ethyl maleimide, propyl Maleimide, butyl maleimide, octyl maleimide, dodecyl maleimide, stearyl maleimide, Phenyl maleimide and N-cyclohexylmaleimide etc..
The vinyl esters of carboxylic acid: for example, vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, octanoic acid Vinyl acetate, vinyl laurate, tertiary ethylene carbonate (vinyl versatate), new vinyl acetate acid, vinyl palmitate, And stearic acid vinyl ester etc..
In addition, ingredient (D) can be that above-mentioned multiple compounds is made to react obtained monomer monomer.For example, can be to make Above-mentioned vinyl esters containing glycidyl and fatty acid response is obtained copolymerizable contains α, β-unsaturated group compound Monomer.It as other examples, can also be to make above-mentioned halogenated alkylstyrene class and be selected from long-chain alcohol, poly- (ethylene oxide) and gather At least one kind of compound containing alcohol hydroxyl group of (ethylene oxide) monoalky lether reacts obtained copolymerizable containing α, β-unsaturation The compound monomer etc. of base.Furthermore, as another example it is sub, it can also be poly- for having for weight average molecular weight (Mw) 200 to 2,000,000 The α that contains of the high molecular weight of object position and ethylene unsaturated double-bond is closed, β-unsaturated group compound monomer is big point that is, so-called Sub- monomer (macromonomer).In the present invention, ingredient (D) is not particularly limited.The 1 of above-mentioned monomer monomer can be only used Kind, alternatively, can also be used in combination a variety of.
Ingredient (E):
Resin combination of the invention can carry out polymerization reaction by irradiating various active energy beams, keep it solid Change.However, above-mentioned resin combination can also be optionally other than the essential component of ingredient (A), (B) and (C1) or (C2) Polymerization initiator containing active energy beam (E).By using active energy beam polymerization initiator (E), polymerization reaction can promote. In an embodiment of the invention, above-mentioned active energy beam is preferably ultraviolet light, is gathered by ultraviolet light irradiation When closing reaction, resin combination preferably contains active energy beam polymerization initiator (E).
In the present invention, as mentioned component (E), it can be used by selecting arbitrary compound as work in well known compound Performance amount ray polymerization initiator.
As concrete example, for example, following substance can be enumerated: 2,2- dimethoxy -2- phenyl acetophenones, acetophenone, hexichol Ketone, xanthone, Fluorenone, benzaldehyde, anthraquinone, 3- methyl acetophenone, 4- chlorobenzophenone, 4,4 '-diaminobenzophenones, Benzoin propyl ether, benzoin ethyl ether, benzil dimethyl ketal, 1- (4- isopropyl phenyl) -2- hydroxy-2-methyl third Alkane-1- ketone, 2- hydroxy-2-methyl-1- phenyl-propane-1- ketone, 4- thioxanthones, camphorquinone and 2- methyl-1-[4- (methyl sulphur Base) phenyl] -2- morpholinopropane -1- ketone etc..
In addition, as commodity, such as following substance can be enumerated: Irgacure 184,907,651,1700,1800,819, 369 and 261 (BASF AG's manufactures)；DAROCUR-TPO (BASF AG's manufacture, 2,4,6- trimethylbenzoyls-hexichol Base-phosphine oxide)；Darocur-1173 (manufacture of Merck company)；Esacure KIP150 and TZT (Japanese Siber Hegner Company's manufacture)；KAYACURE BMS and KAYACURE DMBI (Japanese chemical drug corporation is made) etc..
In addition, it is possible to use intramolecular at least has the poly- initiator of light of 1 (methyl) acryloyl group.
In the present invention, as mentioned component (E), it can be used alone above compound or two or more be applied in combination.
The total amount of resin combination is set as 100 weights from the perspective of reactivity by the mixing ratio of mentioned component (E) Measure part, the preferably range of 0.01 to 20 parts by weight, the more preferably range of 0.5 to 10 parts by weight.
Resin combination of the invention is substantially free of organic solvent.Resin combination is preferably completely free of organic solvent, But above-mentioned active energy beam polymerization initiator (E) is mostly slightly solubility for polymerizable component.Therefore, in order to make active-energy Ray polymerization initiator (E) dissolution, can contain a small amount of organic solvent.The content of organic solvent is preferably 5 weights in resin combination It measures within %.
In addition, the performance boost in order to make above-mentioned active energy beam polymerization initiator (E), can and use active energy beam Sensitizer.As the typical example of active energy beam sensitizer, can enumerate: amine, ureas, sulfur-containing compound, phosphorus-containing compound, Chlorine-containing compound and nitrile or other nitrogenous compounds etc..Wherein it is preferable to use anthracene system or benzophenone series, thioxanthones system Or the compounds such as phenthazine and Bengal rose red.
Ingredient (F):
In an embodiment of invention resin composition, resin combination may be used also other than above-mentioned essential component Siliceous hydride compounds.It can more be mentioned by using silane compound when using resin combination as smears or bonding agent Cementability and adaptation of the height to substrate.And it is easy to improve the heat resistance or humidity resistance of resin layer.
As silane compound (F), well known silane compound can be used, as long as improving the adaptation with aftermentioned substrate Person, there is no particular limitation.Such as it can enumerate: alkyl system alkoxy silane, aryl system alkoxy silane, ethylene base system alkane Oxysilane, amino system alkoxy silane, epoxy alkoxy silane, halogen system alkoxy silane, (methyl) acryloyl base system Alkoxy silane, sulfydryl system alkoxy silane, cationic system alkoxy silane, isocyanates system alkoxy silane etc. have alcoxyl The alkoxyl silicone alkanes and/or hydrogen atom of base are directly in conjunction with silicon atom and with reactive organosilicon alkanes etc..
More specifically, for example, following substance can be enumerated.
Alkyl system alkoxyl silicone alkanes: for example, tetramethoxy-silicane, tetraethoxysilane, tetraisopropoxysilan, methyl Trimethoxy silane, methyltriethoxysilane, three isopropoxy silane of methyl, methyl triacetoxysilane, three (first of methyl Oxygroup ethyoxyl) silane, methyl three (methoxy propoxy) silane, ethyl trimethoxy silane, ethyl triethoxysilane, second Three isopropoxy silane of base, propyl trimethoxy silicane, propyl-triethoxysilicane, three isopropoxy silane of propyl, butyl three Methoxy silane, butyl triethoxysilane, hexyl trimethoxysilane, hexyl triethoxysilane, cyclohexyl trimethoxy Silane, cyclohexyltriethyloxysilane, dimethyldimethoxysil,ne, dimethyl diethoxysilane, dimethyl diisopropyl oxygen Bis- (methoxy ethoxy) silane of base silane, dimethyl 2 acetoxyl group silane, dimethyl, dimethyl are bis- (methoxy propoxy) Silane, diethyldimethoxysilane, diethyldiethoxysilane, diethyl diisopropoxy silane, diethyl diacetyl Oxysilane, Methylethyl dimethoxysilane, Methylethyl diethoxy silane, Methylethyl diisopropoxy silane, first Base ethyl diacetoxy silane, methyl-propyl dimethoxysilane, methyl-propyl diethoxy silane, methyl-propyl diisopropyl Oxysilane and methyl-propyl diacetoxy silane etc..
Aryl system alkoxyl silicone alkanes: for example, phenyltrimethoxysila,e, phenyl triethoxysilane, three isopropyl of phenyl Oxysilane, phenyl triacetoxysilane, tolyl trimethoxy silane and tolyl triethoxysilane etc..
Ethylene base system alkoxy silane class: for example, vinyltrimethoxysilane, vinyltriethoxysilane, ethylene Three isopropoxy silane of base, vinyltriacetoxy silane, vinyl three (methoxy ethoxy) silane, three (first of vinyl Oxygroup propoxyl group) silane, allyltrimethoxysilanis, allyltriethoxysilane, divinyl dimethoxysilane, two Methylvinyldiethoxysilane, divinyl diisopropoxy silane, divinyl diacetoxy silane, methyl ethylene two Methoxy silane and methyl vinyl diethoxysilane etc..
Amino system alkoxyl silicone alkanes: for example, N- (2- amino-ethyl) -3- aminopropylmethyldimethoxysilane, 3- Amino propyl methyl diethoxy silane, N- (2- amino methyl) -3- TSL 8330,3- aminopropyl three Ethoxysilane, N- (2- amino-ethyl) -3- TSL 8330,3-aminopropyltriethoxysilane and N- [2- (vinyl-benzylamino) ethyl] -3- TSL 8330 hydrochloride etc..
Epoxy alkoxyl silicone alkanes: for example, 3- glycidoxypropyltrime,hoxysilane, 3- glycidoxypropyl group Methyl dimethoxysilane, γ-epoxy propoxy propyl triethoxysilane, three ethoxy of β-(3,4- expoxycyclohexyl) ethyl Base silane, 2- (3,4- expoxycyclohexyl) ethyl trimethoxy silane, γ-glycidoxypropyl diethoxy silicon Alkane and β-(3,4- expoxycyclohexyl) ethyl-methyl diethoxy silane etc..
Halogen system alkoxyl silicone alkanes: for example, chloromethyl trimethoxy silane, chloromethyl triethoxysilane, γ-chlorine third Ethyl triethoxy silicane alkane, 3- chloropropyl diethoxy silane etc..
(methyl) acryloyl base system alkoxy silane class: for example, 3- methacryloxypropyl trimethoxy silane, γ-methacryloxypropylmethyl dimethoxysilane, 3- acryloyloxypropyltrimethoxysilane, γ-methyl-prop Alkene methyl dimethoxysilane, γ-methacryloxypropyl methyl diethoxysilane and γ-propylene Methyl dimethoxysilane etc..
Sulfydryl system alkoxyl silicone alkanes: for example, 3-mercaptopropyi trimethoxy silane, 3- mercaptopropyi triethoxysilicane Alkane and γ-mercaptopropyi methyldiethoxysilane etc..
Using isocyanates system alkoxyl silicone alkanes as the alkoxyl silicone alkanes of representative: for example, γ-three second of isocyanates propyl Oxysilane etc..
In addition, can also for example enumerate substance below:
Methyl-monosilane, ethylsilane, dimethylsilane, diethylsilane, phenyldimethylsilane, Butyldimethyl silicon Alkane, di-t-butyl methyl-monosilane, triethylsilane, three hexyl silanes, butyldimethylsilane, cyclohexyldimethyl silane, three Propyl silane, tri isopropyl silane, triisobutyl silane,
Phenyl silane, aminomethyl phenyl silane, dimethylphenylsilaneand, methyl phenyl vinyl silane, dimethyl benzyl silicon Alkane, diphenyl silane,
Methyl dimethoxysilane, dimethoxymethylsilane, methyldiethoxysilane, dimethylethoxysilane, Diethoxy silane, trimethoxy silane, triethoxysilane,
1,1,2- trimethyl disilane, 1,1,2,2- tetraphenyl disilane, 1,1,3,3- tetramethyl-disilazane, three (three Methyl silicane oxygroup) silane, tetramethyl-disilazane, dimetylsilyl dimethyl amine, bis- (dimethylamino) methyl Silane, three (dimethylamino) silane, three (dimetylsilyl) amine,
N, N- dimethylaminomethyl Ethoxysilane, diacetoxy methyl-monosilane, sulfydryl dimethylsilane, cyclopropane Silane, three (trimethyl silyl) silane,
1,1,3,3- tetramethyl-disilazane and
Oily or wax-like organosilicon alkanes with silicyl etc..
Above-mentioned silane compound (F) can be the compound of commodity.In addition, the mixing of two or more silane compound can will be made Object carries out the resulting oligomer system silane compound of oligomeric materialization by hydrolysis and condensation, uses as mentioned component (F).As Mentioned component (F) can be used alone above compound or can also be applied in combination with two or more.
In resin combination of the invention, the mixing ratio of above-mentioned silane compound (F) sets the total amount of resin combination For 100 parts by weight, the preferably range of 0.01 to 10 parts by weight, the more preferably range of 0.1 to 5 parts by weight.Make above-mentioned match When composition and division in a proportion example is more than 0.01 parts by weight, it is easy to get the effect for improving heat resistance or humidity resistance.On the other hand, make it is above-mentioned Mixing ratio is when within 10 parts by weight, due to cohesive force deficiency, and can be in the durability tests such as heat resistance or humidity resistance Inhibit the blistering of polymerization film.In addition, being easy to get excellent pair when using resin combination as smears or bonding agent The adaptation or cementability of substrate.
Other compositions:
Resin combination of the invention can be further containing each in the range of not undermining effect possessed by the present invention Kind additive.In an embodiment of the invention, resin combination can also contain antioxidant other than mentioned component.Pass through Using antioxidant, after the polymerization caused by can inhibit because of active energy beam polymerize film layer through when coloring.
It is not particularly limited, as the concrete example of antioxidant that can be used as commodity and obtain, following substance can be enumerated.
Phenolic antioxidant: for example, ADK STAB AO-50 and ADK STAB AO-80 (Asahi Electro-Chemical Co. Ltd's manufacture) Deng.
Sulfur antioxidant: IRGANOX-PS-800FD (BASF AG's manufacture) etc..
Amine system of being obstructed light stabilizer: TINUBIN 622LD, 144 TINUBIN and TINUBIN 765 (are BASF AG Manufacture) etc..
The mixing ratio of antioxidant, relative to 100 parts by weight of total amount of resin combination, preferably 0.01 to 20 weight Measure the range of part, the more preferably range of 0.01 to 10 parts by weight.It, can when above-mentioned mixing ratio is more than 0.01 parts by weight Inhibit due to active energy beam in the bad situation for being consumed the aggregate rate reduction so as to cause resin combination in early days.It is another Aspect, when above-mentioned mixing ratio is more than 20 parts by weight, aggregate rate is improved, but easily reduces the molecular weight for polymerizeing film.Therefore, By making above-mentioned mixing ratio in 20 parts by weight hereinafter, when using resin combination as smears or bonding agent, can inhibit because The attenuating of polymerization crosslinking film cohesive force and cause durability to reduce.
In the present invention, as long as not undermine the range of effect of the present invention, so that it may form is used according to it, in resin combination In suitably cooperate additive other than antioxidant.For example, being reduced by polymerizing curable shrinking percentage, coefficient of thermal expansion reduces, size is steady It is qualitative improve, elasticity modulus improve, viscosity adjustment, pyroconductivity improve, intensity improve, toughness improve and coloring improve etc. see Point sets out, and can cooperate organic or inorganic filler.Such filler can be made of following substances: polymer, ceramics, metal, gold Belong to the materials such as oxide, metal salt and dye pigment.In addition, about its shape, there is no particular limitation, for example, can be particle shape And threadiness etc..In addition, when cooperating above-mentioned polymer system material, can also make softness-conferring agent, plasticizer, fire retardant, Preserving stabilizer, antioxidant, ultraviolet absorbing agent, thixotropy conferring agents, dispersion stabilizer, mobility donor and defoaming Not as independent filler, and as polymeric blends or polymer alloy, dissolution, half dissolution or micro disperse are being set for agent etc. In oil/fat composition.
Resin combination of the invention, can by by above-mentioned each ingredient according to well known method in the technical field equably It mixes and modulates.Resin combination, can by liquid, paste and it is membranaceous it is any in the form of using in a variety of applications where.Of the invention In one embodiment, above-mentioned resin combination is preferably used in the use of smears or bonding agent on the way.
Resin combination of the invention, preferably according to it using form appropriate adjustment viscosity.Resin combination of the invention Object is preferably substantially free of organic solvent, but as needed, in order to adjust viscosity, it is possible to use solvent.For example, as solvent, It can be used: methanol, ethyl alcohol, isopropanol, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), methyl acetate, ethyl acetate, acetic acid fourth Organic solvents or the water such as ester, hexamethylene, toluene, dimethylbenzene and other hydrocarbon system solvents.By using such solvent, can be easy The viscosity of ground adjustment resin combination.Alternatively, it is also possible to not use solvent, and reduce viscosity by heated resin composition.
In an embodiment of the invention, using resin combination, it is the tree of representative that being formed, which has 0.1 to 6 μm of film thickness, Rouge layer.Therefore, from the perspective of being formed by film, the viscosity of resin combination is preferably at least 1 to 1500mPas model It encloses, preferably 10 to 1300mPas range, and more preferably 20 to 1000mPas range.It is in above-mentioned viscosity When 1500mPas or less, 0.1 to 6 μm of film can be easily formed on substrate by being coated with, is also easy to improve light transmittance Etc. optical characteristics.On the other hand, it when viscosity is 1mPas or more, is easy to control and resin layer is formed by by resin combination Film thickness.
In addition, in another embodiment, using resin combination, forming the resin layer with 6 to 300 μm of film thickness.? When the situation, the viscosity of resin combination, the range of preferably at least 1500 to 100,000mPa s, preferably 3,000 to The range of 50,000mPas.In fact, the viscosity of resin combination is almost determined by the viscosity of oligomer (A).Therefore, lead to Range of the viscosity in 1 to 100,000mPas of management oligomer (A) is crossed, the viscosity of management resin combination is easy.It is above-mentioned The adjustment of embodiment medium viscosity and the coating of resin combination, can be as needed, by adding in above-mentioned resin combination Solvent and easily implement.
Resin combination of the invention is preferably used in the use of smears or bonding agent on the way.Its representative, resin combination Object is coated on the single side of substrate or two sides by the proper method according to well-established law, then makes its solidification, and forms resin layer.Cause This, an embodiment of the invention is related to the resinous combination for having substrate and being arranged on an at least interarea for the substrate The laminated body of the resin layer of object.In present embodiment, the film thickness of resin layer is set according to the purposes of laminated body.
For example, the use in the laminated body used for optical elements such as aftermentioned hard coat film or light polarizing film uses above-mentioned resin combination on the way When object, above-mentioned resin combination is subjected to film coated.It is preferably 0.1 to 6 μ by the thickness that coating is formed by above-mentioned resin layer M, more preferably 0.1 μm to 3 μm.By make resin layer with a thickness of 0.1 μm or more, use resin combination as coating When agent or bonding agent, it is easy to get sufficient adaptation or bonding force.On the other hand, most when resin layer thickness is more than 6 μm Situation is the variation in terms of having not seen the characteristics such as adaptation or bonding force.
In addition, by above-mentioned resin combination use in the member such as aftermentioned plus decorating film (referring to touch panel filler piece) optics Part laminated body use on the way when, by above-mentioned resin combination carry out thick film coating.Above-mentioned resin layer is formed by by coating Thickness be preferably 6 to 300 μm, more preferably 20 μm to 250 μm.By make resin layer with a thickness of 6 μm or more, use resin When composition is as smears or bonding agent, other than the filling function of touch panel, it is slow to be also easy to get sufficient stress And property.On the other hand, by make resin composition layer with a thickness of 300 μm hereinafter, being easy to inhibit to apply trace the coatings such as occurs It reduces.
The coating method of above-mentioned resin combination, there is no particular limitation.For example, wire rod (mayer can be applicable in Bar), applicator (applicator), hairbrush, sprayer, roller, gravure coater, die coating machine, micro- gravure coater, die lip apply Known in cloth machine, chipping wheel coater (comma coater), curtain coater, knife type coater, reverse coating machine, spin coater etc. Various methods.In addition, the form about film coated or thick film coating etc., also visual purposes, selects without particular limitationly.
Resin combination of the invention can be coated on substrate by well known conventional process, then, by institute's shape At coating layer irradiate active energy beam, carry out containing α, the polymerization reaction of β-unsaturated bond base compound, to form solidification Object.In an embodiment of the invention, active energy beam is preferably with 150 to the 550nm wavelength regions comprising ultraviolet light Based on light energy.As the light source appropriate of such light energy is provided, can enumerate: low pressure mercury lamp, medium pressure mercury lamp, high-pressure mercury Lamp, ultrahigh pressure mercury lamp, chemical lamp (chemical lamp), black light lamp (black light lamp), microwave-excited mercury lamp, LED Lamp, xenon lamp and metal halide lamp etc..In addition, laser beam and electron beam can also be used in another embodiment of the present invention Deng the active energy beam as exposure.
The exposure intensity of active energy beam, preferably 10 to 500mW/cm2.It is less than 10mW/cm in photo-irradiation intensity2 When, solidification needs for a long time, more than 500mW/cm2When, because of the heat that lamp is radiated, have that substrates deterioration occurs for various substrates can Energy property, therefore not preferably.Accumulative exposure, preferably 50 to 5,000mJ/ represented by the product of exposure intensity and irradiation time cm2.It is lower than 50mJ/cm in accumulative exposure2When, polymerizing curable needs for a long time, be higher than 5,000mJ/cm2When, irradiation time Become extremely long, and productivity is made to be deteriorated, therefore not preferably.Representative active energy beam polymer resin composition, generally Need 1000mJ/cm2Above accumulative exposure.But the above-mentioned resin combination in the present invention, even if being less than 1000mJ/cm2 Low accumulative exposure when also polymerize well.
In laminated body of the invention, resin layer on substrate is to make above-mentioned resin combination by the irradiation of active energy beam Object polymerizing curable and former, substantially with -80 DEG C to 100 DEG C of glass transition temperature (hereinafter referred to as Tg).By above-mentioned laminated body Punching processing from the perspective of, the Tg of resin layer, to be ranged preferably from -60 DEG C to 40 DEG C, at -60 DEG C to 0 DEG C Range is more preferably.
By above-mentioned viewpoint, in an embodiment of the invention, resin combination is preferably constituted as follows: in order to make to set The Tg of rouge layer (the polymerizing curable object of resin combination) has 1 or more within the above range, with (A) oligomer, (B) intramolecular Carboxyl contains α, and β-unsaturated double-bond base compound, (C1) cyclic imines or (C2) carbodiimide compound are necessary Ingredient, also, as needed and be appropriately chosen point (D) intramolecular it is not carboxylic contain α, β-unsaturated double-bond base chemical combination Object, (E) polymerization initiator and (F) silane compound etc. add ingredient.In the embodiment, as mentioned component (B) and (D) α, β-unsaturated double-bond base, preferably respectively using have (methyl) acryloyl group compound, more preferably using have propylene The compound of acyl group.
In an embodiment of the invention, resin combination as active energy beam polymerism smears (hereinafter, Referred to as smears) it uses, resin combination forms the coating layer of the single or double of covering substrate.It is above-mentioned in the embodiment Substrate can be timber, metal plate, plastic plate, film-like substrate, glass plate, paper conversion product etc., can use with being not particularly limited These substances.
On the other hand, in another embodiment of the present invention, resin combination is bonded as active energy beam polymerism Agent (hereinafter referred to as bonding agent) uses, and resin combination forms the adhesive layer of fitting 2 or more substrate.In this embodiment, In order to which the irradiation by active energy beam carries out polymerization reaction, what above-mentioned substrate must be readily penetrated through by active energy beam Material is constituted.As above-mentioned base material, hyaline membrane or transparency glass plate are particularly preferably used.If but using hyaline membrane or transparent glass Glass plate is as a wherein substrate, then the substrate that can also be used active energy beam to be not easy to penetrate, such as by timber, metal plate, modeling The substrate that the materials such as flitch, paper conversion product are constituted is as another substrate.It, can be by from hyaline membrane or transparency glass plate when the situation Active energy beam is irradiated in side, and carries out the polymerizing curable of resin combination.
, it is preferable to use film-like substrate is as substrate in laminated body of the invention.As the concrete example of film-like substrate, can enumerate Celo sweet smell (cellophane), various plastic foils and paper etc..Wherein, it is preferable to use transparent various plastic foils.In addition, conduct Film-like substrate can be single layer structure, can also have multilayered structure made of the stacking of multiple substrates, have as long as film is transparent The film of any structure can be suitble to use.When constituting laminated body of the invention, preferably formed in at least one side of hyaline membrane Resin layer containing invention resin composition.
Hereinafter, the more specific embodiment of laminated body of the present invention is directed to, to use hyaline membrane as the situation of substrate It is illustrated.That is, the following description is related to having on an at least interarea for hyaline membrane by resin combination institute structure of the invention At the resin layer for being known as coating layer or adhesive layer laminated body.
The laminated body for using resin combination of the invention to be constituted as smears, representative, for hyaline membrane/ Coating layer or coating layer/hyaline membrane/coating layer structure laminar film.Such laminated body can be by least the one of hyaline membrane It is coated with resin combination on interarea, then makes the resin layer polymerizing curable, forms coating layer and obtains.
On the other hand, the laminated body for using resin combination of the invention to be constituted as bonding agent, representative are Multiple hyaline membranes are laminated as bright film/adhesive layer/hyaline membrane or hyaline membrane/adhesive layer/hyaline membrane/adhesive layer/hyaline membrane Obtained sheet form multilaminate film.In addition, in other forms, laminated body also can have by hyaline membrane/adhesive layer/hyaline membrane/ Sheet form multilaminate film as adhesive layer/hyaline membrane/adhesive layer/hyaline membrane is fixed on other light as glass or optical forming body Learn the composition on component.Above-mentioned laminated body can be such that adhesive layer solidifies by the single side or double-sided illumination active energy beam from film And it obtains.
When using above-mentioned resin combination as smears or bonding agent, the polymerizing curable of resin combination can be by setting When the coating of oil/fat composition, in the stacking of film or after stacking, active energy beam is irradiated to coating layer and is implemented.Without especially limit It is fixed, but above-mentioned irradiation is preferably implemented after the stacking of film etc..
As described above, above-mentioned laminated body may be adapted to using in optical applications when using hyaline membrane as substrate.By To from the perspective of good optical characteristics, hyaline membrane used in above-mentioned laminated body, for example, it is preferable to for by the transparency, machine The thermoplastic resin of the excellent optical characteristics such as tool intensity, thermal stability, moisture barrier performance and isotropism is constituted various Bright film.Such various hyaline membranes are also referred to as various plastic foils or plastic sheet.As concrete example, for example, polyvinyl alcohol film, poly- three Acetylcellulose film, the polyolefin mesenteries such as polypropylene, polyethylene, polycyclic alkene and vinyl-vinyl acetate copolymer are gathered The polyester mesentery such as ethylene terephthalate and polybutylene terephthalate, polycarbonate mesentery, gather polynorbornene mesentery Aromatic ester mesentery, polyacrylic acid mesentery, polyphenylene sulfide mesentery, polystyrene mesentery, polyvinyl mesentery, polyamide mesentery, polyamides Imines mesentery and polyethylene oxide mesentery etc..
In laminated body of the invention, when being laminated by multiple hyaline membranes and constituting multilayer film, used hyaline membrane can be Same composition, can also be different.For example, can on polycyclic alkene mesentery across adhesive layer and laminated polypropylene acid mesentery.
The thickness of hyaline membrane can suitably determine, and generally be gone out by viewpoints such as the workability such as intensity or operability and thin layers Hair is 1 to 500 μm, preferably 1 to 300 μm, more preferably 5 to 200 μm.In optical applications, the thickness of hyaline membrane is especially suitable Preferably 5 to 150 μm of range.
, it is preferable to use mainly being used in optical applications in one embodiment of laminated body used for optical elements of the invention Optical film as above-mentioned hyaline membrane.Here, so-called optical film is imposed made of specially treated to above-mentioned hyaline membrane itself Film, it is desirable to which there is light to penetrate the optics sexual functions such as light diffusion, optically focused, refraction, scattering and HAZE.Such optical film can individually, Or it is used with Several combinations.It, can be by being formed on an at least interarea for above-mentioned optical film in an embodiment of the invention Resin layer containing above-mentioned resin combination and constitute laminated body used for optical elements.
As the concrete example of above-mentioned laminated body used for optical elements, for example, hard coat film, antistatic films, anti-glare can be enumerated Film, phase difference film, elliptical polarized light film, anti-reflective film, optical diffusion film, promotes brightness film, prism film (also referred to as rib at light polarizing film Eyeglass) plus decorating film (referring to touch panel filler piece) and light guiding film (also referred to as light guide plate) etc..Tree of the invention can be used Oil/fat composition is further attached to liquid crystal display device, PDP module, touching as bonding agent, by above-mentioned laminated body used for optical elements On the glass plate for controlling panel module and organic EL module etc..In addition, resin group of the invention can be used as other form Object is closed as bonding agent, above-mentioned laminated body used for optical elements is attached on above-mentioned various optical films.
Hereinafter, enumerating an example of light polarizing film as laminated body used for optical elements, the embodiment of above-mentioned laminated body is had more Body it is illustrated.Light polarizing film is also referred to as polarizer, is the optics with the multilayered structure for being clamped polarizer with 2 films Film.In above-mentioned light polarizing film, when hyaline membrane is arranged in the two sides of polarizer, the saturating of the material containing same polymer can be used in table Bright film, or the hyaline membrane containing different polymer materials etc. can also be used.Light polarizing film is for example with using fine as 2 poly- acetyl group The poly- tri acetyl cellulose system protective film (hereinafter referred to as " TAC film ") of prime system film is tieed up by the two of polyethenol series polarizer The structure that face is clamped.As other examples, light polarizing film has using polycyclic alkene mesentery, the polypropylene as polynorbornene mesentery The structure that the films such as sour mesentery, polycarbonate mesentery and polyester mesentery clamp the one or two sides of polyethenol series polarizer.
It is not particularly limited, for example, above-mentioned polarizer (light polarizing film) can be manufactured such as following manner.
(I) on an interarea of the 1st hyaline membrane (the 1st protective film), coating invention resin composition as bonding agent, Form the 1st polymerism adhesive layer.In addition, being coated with resin group of the present invention on an interarea of the 2nd hyaline membrane (the 2nd protective film) Object is closed as bonding agent, forms the 2nd polymerism adhesive layer.Then, above-mentioned 1st polymerism adhesive layer and the 2nd polymerism are bonded Layer simultaneously/or sequentially overlap on two interareas of polyethenol series polarizer.Then, activity is irradiated to obtained laminated body Energy-ray makes the 1st and the 2nd adhesive layer polymerizing curable.
(II) on an interarea of polyethenol series polarizer, coating invention resin composition as bonding agent, The 1st polymerism adhesive layer is formed, by the surface of the 1st polymerism adhesive layer with the 1st hyaline membrane (the 1st protective film) covering.It connects , on another interarea of polyethenol series polarizer, coating invention resin composition forms the 2nd as bonding agent Polymerism adhesive layer covers on the surface of the 2nd polymerism adhesive layer with the 2nd protective film.Later, obtained laminated body is shone Active energy beam is penetrated, the 1st and the 2nd polymerism adhesive layer polymerizing curable is made.
(III) it will drip respectively as the invention resin composition of bonding agent in the 1st hyaline membrane (the 1st protective film) one The end of polyethenol series polarizer is laminated on a interarea and on the another side upper layer of above-mentioned polyethenol series polarizer It is laminated with the end of the 2nd protective film, between making the laminated body pass through roller, and sprawls the bonding agent of each interlayer.Then, to stacking Body irradiates active energy beam, makes active energy beam polymerism bonding agent polymerizing curable.
More than, as an embodiment of laminated body used for optical elements, enumerates light polarizing film and be illustrated as an example.But In above-mentioned laminated body, use invention resin composition characterized by smears or bonding agent using to various substrates.Therefore, It should be readily understood that are as follows: it is not limited to light polarizing film, in the other embodiments using other various substrates, also may make up and be suitable for The laminated body used in optical applications.
Embodiment
Hereinafter, being illustrated for the present invention according to specific embodiment.But the present invention is not limited to implementations below Example.In addition, " part " and " % " for recording in following Examples and Comparative Examples, respectively indicates " parts by weight " and " weight % ",
The modulation of 1-1. resin combination
(coordinating example 101 to 127)
It is replaced into 10% or less and the 300ml mayonnaise bottle by shading in oxygen concentration, respectively to compare shown in table 1 Rate addition: intramolecular at least has 1 or more α, and β-unsaturated double-bond base oligomer (A), intramolecular have 1 or more carboxyl Contain α, β-unsaturated double-bond base compound monomer (B), cyclic imines (C1), intramolecular it is not carboxylic contain α, β- Compound monomer (D), active energy beam polymerization initiator (E) and the silane compound (F) of unsaturated double-bond base.Then, make With blender (" T.K.HOMO DISPER " that special machine chemical industry company manufactures), it is sufficiently stirred and abundant deaeration, thus Obtain the resin combination of each coordinating example shown in table 1.
[table 1]
The detail of documented each ingredient is as follows in table 1.In table 1, mark "-" indicates unmated.
Ingredient (A)
Purple light UV 3000B: Nippon Synthetic Chemical Industry Co.'s manufacture, polyurethane series oligomer (urethane acrylates Ester), Mw=18000.
The manufacture of Ebecryl 8402:DAICEL-CYTEC company, aliphatic carbamate acrylate, Mw=1000.
The manufacture of UN-6301: Gen Shang industrial group of Art Resin, urethane acrylate oligomer, Mw= 30000。
The manufacture of Ebecryl 885:DAICEL-CYTEC company, polyester acrylate, Mw=6000.
The manufacture of Ebecryl 853:DAICEL-CYTEC company, polyester acrylate, Mw=470.
Ingredient (B)
AA: acrylic acid, AV=780
M-5300: the manufacture of East Asia Synesis Company, acid esters containing acid propylene, AV=200
Ingredient (C1)
The bis- hydroxymethyl butanol three [3- (1- aziridinyl) propionic ester] of HBAP:2,2-
The bis- hydroxymethyl butanol three [3- (2- methyl-1-aziridinyl) propionic ester] of HBMAP:2,2-
HDU:1,6- hexamethylene bis-N, N '-ethylene urea
Ingredient (D)
4HBA: acrylic acid -4- hydroxybutyl
HEA: 2-Hydroxy ethyl acrylate
IBXA: isobornyl acrylate
ACMO:N- acryloyl morpholine
Ingredient (E)
TPO:2,4,6- trimethylbenzoy-diphenies-phosphine oxide (BASF AG's manufacture, DAROCUR TPO)
Ingredient (F)
KBM-5103: the manufacture of chemical company of SHIN-ETSU HANTOTAI, silane compound
In the present invention, the excellent resin combination of various characteristics is constituted while mentioned component can be not limited to.
The weight average molecular weight (Mw) of mentioned component (A) used in the resin combination of each coordinating example shown in table 1, And the acid value (AV) of ingredient (B), it is the value determined according to the following method.
< molecular weight >
The measurement of weight average molecular weight (Mw), the GPC (gel permeation chromatograph) manufactured using Showa electrician company " Shodex GPC System-21 " is implemented.GPC is that the difference for matter utilization its molecular size being dissolved in solvent is divided From quantitative liquid chromatograph.Use tetrahydrofuran as solvent.The value of documented weight average molecular weight Mw is changed for polystyrene Calculation value.In addition, can also be determined according to same method about number-average molecular weight (Mn).
< acid value (AV) >
In tool plug conical flask, precision weighs the compound monomer (B) that about 1g is used as raw material, adds toluene/second Alcohol (volume ratio: toluene/ethanol=2/1) mixed liquor 100ml simultaneously dissolves.In the solution, addition phenolphthalein test solution as indicator, And it is kept for 30 seconds.Later, with the titration of 0.1N alcohol potassium hydroxide solution, until solution is in pale red.Then, according to following Formula finds out acid value (mg KOH/g), the value as resin drying regime.
Acid value (mg KOH/g)={ (5.611 × a × F)/S }/(nonvolatile component concentration/100)
Wherein, S: the amount of weighing (g) of sample
The consumption (ml) of a:0.1N alcohol potassium hydroxide solution
The power valence of F:0.1N alcohol potassium hydroxide solution
In addition, hydroxyl value can be determined by the method for following record in used oligomer (A) hydroxyl.
< hydroxyl value (OHV) >
Precision weighs about 1g sample in tool plug conical flask, adds toluene/ethanol (capacity ratio: toluene/ethanol=2/1) Mixed liquor 100ml simultaneously dissolves.Accurately acetic anhydride 25g (is dissolved in pyridine, makes its capacity 100ml by addition acetylizing agent again Solution) 5ml, and stir about 1 hour.Addition phenolphthalein test solution is as indicator thereto, and is kept for 30 seconds.Later, with 0.1N Alcohol potassium hydroxide solution is titrated to solution in until pale red.
Hydroxyl value is found out according to following formula.The hydroxyl value is the value (unit: mg KOH/g) of resin drying regime.
Hydroxyl value (mg KOH/g)=[{ (b-a) × F × 28.25 }/S]/(nonvolatile component concentration/100)+D
Wherein, S: the amount of weighing (g) of sample
The consumption (ml) of a:0.1N alcohol potassium hydroxide solution
B: the consumption (ml) of the 0.1N alcohol potassium hydroxide solution of blank test
The titer of F:0.1N alcohol potassium hydroxide solution
D: acid value (mg KOH/g)
For the resin combination of each coordinating example shown in table 1, according to the following method determine solution appearance, viscosity and Glass transition temperature (Tg).The results are shown in Table 2 for it.
< appearance >
With the liquid appearance of the resin combination of each coordinating example shown in visual valuation table 1.
< viscosity >
Use the resin combination of each coordinating example of about 1.2ml as measurement sample.In the environment of 23 DEG C, E type is used Viscosimeter (TV-22 of Dong Ji industry companies manufacture) is surveyed under conditions of rotation speed 0.5 to 100rpm, rotation 1 minute It is fixed, find out solution viscosity (mPas).
< glass transition temperature (Tg) >
By " SSC 5200Disc Station " (manufacture of Seiko instrument company) and Robot DSC (differential scanning calorimeter, " RDC220 " of Seiko instrument company manufacture) connection, it is used for measurement.
The resin combination of each coordinating example shown in table 1 is coated on the polyester film by lift-off processing, then irradiates work Property energy-ray, makes its polymerizing curable.Obtained solidfied material about 10mg is removed, is placed in aluminium dish as sample, by weighing Device is on differential scanning calorimeter afterwards.On the other hand, it will not be placed in the homotype aluminium dish of sample as reference.By the aluminium dish of two sides After 100 DEG C of temperature heat 5 minutes, handled with liquid nitrogen rapid cooling to -120 DEG C.Later, it is heated up with 10 DEG C/min, by Obtained DSC line chart in heating, decision glass transition temperature (Tg, unit: DEG C).
[table 2]
The manufacture of 1-2. laminated body
(embodiment A1 to A22 and Comparative examples A 1 to A7)
The resin combination for each coordinating example modulated before using has protective film as bonding agent, such as following manner manufacture (1)/adhesive layer/PVA system polarizer/adhesive layer/protective film (2) structure laminated body.
In above-mentioned laminated body, as protective film (1), poly- three containing ultraviolet absorbing agent manufactured using Fuji Photo Film Co., Ltd. Acetylcellulose mesentery: trade name " FUJITAC:80 μm ".In addition, being supplied as protective film (2) using Fujiphoto commodity The poly- tri acetyl cellulose mesentery without ultraviolet absorbing agent of Ying company manufacture: trade name " 50 μ of TAC " (50 μm of thickness). Protective film (1) and (2) are hyaline membrane.
Firstly, to each film surface, with 300Wmin/m2Discharge capacity carry out sided corona treatment.After carrying out the surface treatment Within 1 hour, the resin combination of each coordinating example is coated in each film surface using bar coater, forms 4 μm of film thickness of bonding Layer.Then, in a manner of clamping polyethenol series polarizer, above-mentioned surface treated protective film (1) and (2) are attached. So after operation, obtain containing protective film (1)/adhesive layer/PVA system polarizer/adhesive layer/protective film (2) laminated body.
Then, in such a way that protective film (1) is connected to terneplate, the four directions of the laminated body is consolidated with celo sweet smell adhesive tape It is fixed, it is fixed on terneplate.Then, using active energy beam irradiation unit (Toshiba manufacture, high-pressure sodium lamp), with Maximal illumination 300mW/cm2, accumulative light quantity 300mJ/cm2Condition, from protective film (2) side irradiate ultraviolet light, make be bonded layers of polymer Solidification.So operate the function that obtained laminated body has polarizer.
To the obtained laminated body (polarizer), peel strength is found out according to the following method, gel fraction, punching add Work, shrinking percentage, heat resistance and humidity resistance.The results are shown in Table 3 for it.
< peel strength >
Bonding force is according to JIS K6854-4 bonding agent-removing adhesive strength test method(s)-the 4: dance roller method carries out Measurement.That is, obtained polarizer is cut into 25mm × 150mm size with cutter (cutter), make as test sample With.On the two sides of the test sample, metal plate is attached by adhesive tape (TOYOCHEM company manufactures, DF 8712S), is obtained To the measurement laminated body being made of polarizer and metal plate.In the measurement in laminated body (polarizer), protecting in advance Stripping portion is set between film and polarizer.Under conditions of 23 DEG C, relative humidity 50%, with 300mm/ minutes speed by upper It states stripping portion and peels the measurement laminated body, and measure peeling force.At this point, the measurement of peeling force is to polyethenol series polarizing It is implemented both between mirror and protective film (1) and between polyethenol series polarizer and protective film (2).With the peeling force As bonding force, evaluated according to evaluation criteria below.It is in actual use without special when being evaluated as " C " or more Problem.
(evaluation criteria)
A: not peelable or polarizer destroys
B: peeling force is 2.0 (N/25mm) more than and less than 5.0 (N/25mm).
C: peeling force is 1.0 (N/25mm) more than and less than 2.0 (N/25mm).
D: peeling force is less than 1.0 (N/25mm).
< gel fraction >
In polynorbornene mesentery (trade name " the ZEONOR ZF- for the Japanese ZEON company manufacture for not implementing sided corona treatment 14:100 μm ") on, using bar coater, the resin combination recorded in each coordinating example is coated with as bonding agent, forms film thickness 20 to 25 μm of polymerism adhesive layer.In addition, stacking does not impose the ZEONOR of sided corona treatment on above-mentioned polymerism adhesive layer ZF-14 obtains having hyaline membrane/polymerism adhesive layer/hyaline membrane 3-tier architecture laminated body.Later, using active-energy Beam exposure apparatus (Toshiba's manufacture, high-pressure sodium lamp), with maximal illumination 300mW/cm2, accumulative light quantity 300mJ/cm2Item Part irradiates active energy beam, makes above-mentioned polymerism adhesive layer polymerizing curable.Then, by the laminated body of obtained 3-tier architecture Hyaline membrane (ZEONOR ZF-14) is removed respectively, obtains adhesive layer.The weight (weight 1) of the adhesive layer is measured, then, Adhesive layer is clipped between metal mesh (mesh) and metal mesh, maintains adhesive layer not to be laminated, in methyl ethyl ketone (MEK) Reflux 3 hours.Later, after 30 minutes dry under the conditions of 80 DEG C of temperature, the weight (weight 2) of adhesive layer is measured.By this A little values are used for following formula, so as to find out gel fraction.
Gel fraction (%)={ 1- (weight 1- weight 2)/weight 1 } × 100
Further, it is evaluated according to evaluation criteria below.It is to actually use upper nothing if being evaluated as " B " or more The grade of problem.
(evaluation criteria)
A: gel fraction is 90% or more
B: gel fraction is 80% less than 90%
C: gel fraction is less than 80%
< punching processing >
It, will be inclined made by each embodiment and each comparative example using the knife for 100mm × 100mm that Dumbbell company manufactures Tabula rasa is from protective film (1) side punching.With the peel distance on polarizer periphery of the gage measurement through punching, and according to evaluation below Benchmark is evaluated.It is the grade for actually using upper no problem if being evaluated as " C " or more.
(evaluation criteria)
A:0mm
B:1mm or less
C:1 to 3mm
D:3mm or more
< shrinking percentage >
Above-mentioned polarizer small pieces are placed in the constant temperature and humidity machine of 60 DEG C of-dry and 60 DEG C of -90RH%, are measured 60 hours The shrinkage of extending direction afterwards finds out shrinkage relative to the ratio of raw footage (100mm) as shrinking percentage, and according to below Evaluation criteria is evaluated.It is the grade for actually using upper no problem if being evaluated as " B " or more.In addition, so-called " dry ", It is the experimental condition in the baking oven for having humidity adjustment function, when only controlling temperature, not controlling humidity.
(evaluation criteria)
A: shrinking percentage is 0.2% or less
B: shrinkage ratio 0.2% is big and is 0.4% or less
C: shrinking percentage is more than 0.4%.
< heat resistance >
By embodiment A1 to A22 and Comparative examples A 1, into A7, obtained each polarizer cuts into 50mm × 40mm size, Under conditions of 80 DEG C of-dry and 100 DEG C of-dry, respectively expose to the open air 1000 hours.Confirmation, which exposes rear polarizer end to the open air, by visual observation has Without removing, evaluated according to evaluation criteria below.If being evaluated as " C " or more, no problem in actual use Grade.
(evaluation criteria)
A: entirely without removing under conditions of 100 DEG C of-dry.
B: entirely without removing under conditions of 80 DEG C of-dry.
C: there is the removing less than 1mm under conditions of 80 DEG C of-dry.
D: there is the removing of 1mm or more under conditions of 80 DEG C of-dry.
< humidity resistance >
Embodiment A1 to A22 and Comparative examples A 1 to the obtained each polarizer of A7 are cut into 50mm × 40mm size, in It is exposed to the open air 1000 hours under conditions of 60 DEG C of -90%RH and under conditions of 85 DEG C of -85%RH.Confirmation exposes rear polarisation to the open air by visual observation Whether there is or not removings for the end of plate, are evaluated according to evaluation criteria below.It is in actual use if being evaluated as " C " or more The grade of no problem.
(evaluation criteria)
A: entirely without removing under conditions of 85 DEG C of -85%RH.
B: entirely without removing under conditions of 60 DEG C of -90%RH.
C: there is the removing less than 1mm under conditions of 60 DEG C of -90%RH.
D: there is the removing of 1mm or more under conditions of 60 DEG C of -90%RH.
[table 3]
The detail for the optical film recorded in table 3 is as follows.
ZF-14: the polynorbornene mesentery of Japanese ZEON company manufacture, 100 μm of film thickness.
HBD-002: the polyacrylic acid mesentery of Mitsubishi's Li Yang company manufacture, 50 μm of film thickness.
(embodiment B1 to B25 and comparative example B1 to B7)
As active energy beam polymerism smears, using the resin combination of each coordinating example shown in table 1 and table 2, Following operation, manufactures the laminated body with optical film/coating oxidant layer structure.In above-mentioned laminated body, as optical film, richness is used The poly- tri acetyl cellulose mesentery containing ultraviolet absorbing agent of scholar's film company manufacture: trade name " FUJITAC:80 μm ".It is first First, to the optics film surface, with 300Wmin/m2Discharge capacity carry out sided corona treatment.1 hour after carrying out the surface treatment Within, using bar coater, it is coated with the resin combination of each coordinating example on the surface of the film, forms 4 μm of film thickness of polymerism and applies Cloth oxidant layer.
Then, in such a way that optical film is connected to terneplate, the four directions of above-mentioned laminated body is consolidated with celo sweet smell adhesive tape It is scheduled on terneplate.Then, it will be replaced in UV irradiation unit (Toshiba manufactures, high-pressure sodium lamp) with dry nitrogen Afterwards, with the maximal illumination 300mW/cm of wavelength 365nm2, accumulative light quantity 300mJ/cm2Condition, from above-mentioned polymerism smears Ultraviolet light is irradiated in layer side, makes its polymerizing curable, obtains the laminated body with coating oxidant layer.To so operating obtained stacking Body finds out closing force, heat resistance according to the following method.The results are shown in Table 4 for it.
< closing force >
According to JIS K5400, implement gridiron pattern disbonded test.By the block number removed in 100 pieces, according to evaluation base below Standard is evaluated.It is the grade for actually using upper no problem if being evaluated as " C " or more.
(evaluation criteria)
A:0 block
B:1 to 10 pieces
C:11 to 30 pieces
It is more than D:31 block
< heat resistance >
By embodiment B1 to B25 and comparative example B1, into B7, obtained laminated body cuts into 50mm × 40mm size, in It is exposed to the open air under conditions of 80 DEG C of-dry 1000 hours.To the laminated body after exposing to the open air, judge by visual observation end whether there is or not removing, according to Under evaluation criteria evaluated.It is the grade for actually using upper no problem if being evaluated as " B " or more.
(evaluation criteria)
A: entirely without removing.
B: there is the removing less than 1mm.
C: there is the removing of 1mm or more.
[table 4]
The detail for the optical film recorded in table 4 is as follows.
FUJITAC: the TAC mesentery (80 μm) containing ultraviolet absorbing agent of Fuji Photo Film Co., Ltd.'s manufacture.
ZF-14: the polynorbornene mesentery (100 μm) without ultraviolet absorbing agent of Japanese ZEON company manufacture.
HBD-002: the polyacrylic acid mesentery (50 μm) without ultraviolet absorbing agent of Mitsubishi's Li Yang company manufacture.
The polycarbonate mesentery (43 μm) without ultraviolet absorbing agent of R-140:Kaneka company manufacture.
The polyester mesentery (50 μm) containing ultraviolet absorbing agent of Emblet S:Unitika company manufacture.
The polyethylene mesentery (50 μm) containing ultraviolet absorbing agent of TUX-HZ:Tohcello company manufacture.
In the present invention, it is not limited to above-mentioned optical film, various optical films can be used to constitute the excellent layer of various characteristics Stack.
When as above using invention resin composition as active energy beam polymerism bonding agent, as shown in table 3, Embodiment A1, though viscosity has a little high, has no special problem into A22, may make up excellent stacking in terms of various characteristics Body.In contrast, in Comparative examples A 1 into A7, it is known that especially bonding force reduces, also poor in terms of punching processing, shrinking percentage. In addition, when using resin combination of the invention as active energy beam polymerism smears, also show with shown in table 3 As a result same tendency.That is, as shown in table 4, for embodiment B1 into B25, closing force and heat resistance are excellent, it can be without especially asking Topic ground constitutes laminated body.In contrast, in comparative example B1 into B7, it is known that lack closing force and heat resistance, it is especially therein Either one is all particularly poor.
The modulation of 2-1. resin combination
(coordinating example 201 to 230)
It is replaced into 10% or less and the 300ml mayonnaise bottle by shading in oxygen concentration, respectively to compare shown in table 5 Rate addition: intramolecular at least has 1 or more α, and β-unsaturated double-bond base oligomer (A), intramolecular have 1 or more carboxyl Contain α, β-unsaturated double-bond base compound (B), carbodiimide compound (C2), intramolecular it is not carboxylic contain α, β-insatiable hunger With the compound (D), active energy beam polymerization initiator (E) and silane compound (F) of double bond base.Then, using blender (special machine chemical industry company manufacture, " T. K.HOMO DISPER "), is sufficiently stirred and abundant deaeration, to obtain table 5 The resin combination of shown each coordinating example.
[table 5]
The detail of documented each ingredient is as follows in table 5.In table 5, mark "-" indicates unmated.
Ingredient (A)
Purple light UV 3000B: Nippon Synthetic Chemical Industry Co.'s manufacture, polyurethane series oligomer (urethane acrylates Ester).
The manufacture of Ebecryl 8402:DAICEL-CYTEC company, aliphatic carbamate acrylate, Mw=1000.
The manufacture of UN-6301: Gen Shang industrial group of Art Resin, urethane acrylate oligomer, Mw= 30000。
The manufacture of Ebecryl 885:DAICEL-CYTEC company, polyester acrylate, Mw=6000.
The manufacture of Ebecryl 853:DAICEL-CYTEC company, polyester acrylate, Mw=470.
Ingredient (B)
AA: acrylic acid, AV=780.
M-5300: the manufacture of East Asia Synesis Company, acid esters containing acid propylene, AV=200
Ingredient (C2)
DCC:N, N '-dicyclohexylcarbodiimide.
DIC:N, N '-diisopropylcarbodiimide.
DPC:1,3- diphenyl carbodiimide.
Ingredient (D)
4HBA: acrylic acid -4- hydroxybutyl.
HEA: 2-Hydroxy ethyl acrylate.
IBXA: isobornyl acrylate.
ACMO:N- acryloyl morpholine
Ingredient (E)
TPO:2,4,6- trimethylbenzoy-diphenies-phosphine oxide (BASF AG's manufacture, DAROCUR TPO).
Ingredient (F)
KBM-5103: the manufacture of chemical company of SHIN-ETSU HANTOTAI, silane coupling agent (3- acryloyloxypropyltrimethoxysilane).
The manufacture of A-174:TANAC company, silane coupling agent (γ-methacryloxypropyl trimethoxy silane).
Sensitizer: DETX-S (Japanese chemical drug corporation is made, thioxanthones system sensitizer (2,4- diethyl thioxanthone)).
Antioxidant: AO-50, ADEKA company manufacture.
In the present invention, it is not limited to mentioned component, may make up the excellent resin combination of various characteristics.
It is determined in the same manner as the method illustrated in the past upper used in the resin combination of each coordinating example shown in table 5 State the weight average molecular weight (Mw) of ingredient (A) and the acid value (AV) of ingredient (B).In addition, for the solution appearance of each resin combination (hereinafter, sometimes referred to simply as appearance), viscosity and glass transition temperature (Tg), also determine in the same manner as the method illustrated in the past.It is tied Fruit is as shown in table 6.
[table 6]
The manufacture of 2-2. laminated body
(embodiment C1 to C28 and comparative example C1 to C4)
Use the resin combination for each coordinating example modulated in the past as bonding agent, following manufacture have protective film (1)/ Adhesive layer/PVA system polarizer/adhesive layer/protective film (2) structure laminated body.
In above-mentioned laminated body, as protective film (1), manufactured using Japanese ZEON company poly- without ultraviolet absorbing agent Norbornene mesentery: trade name " ZF-14:100 μm ".In addition, being manufactured not as protective film (2) using Mitsubishi's Li Yang company Polyacrylic acid mesentery containing ultraviolet absorbing agent: trade name " HBD-002 " (50 μm of thickness).That is, protective film (1) and (2) are Hyaline membrane.
Firstly, to each film surface, with 300Wmin/m2Discharge capacity carry out sided corona treatment.After carrying out the surface treatment Within 1 hour, the resin combination of each coordinating example is coated in each film surface using bar coater, forms 4 μm of film thickness Polymerism adhesive layer.Then, above-mentioned surface treated protective film is attached in a manner of clamping polyethenol series polarizer. So after operation, obtain containing protective film (1)/adhesive layer/PVA system polarizer/adhesive layer/protective film (2) laminated body.
Then, in such a way that protective film (1) is connected to terneplate, the four directions of the laminated body is consolidated with celo sweet smell adhesive tape It is fixed, it is fixed on terneplate.Then, using active energy beam irradiation unit (Toshiba manufacture, high-pressure sodium lamp), with Maximal illumination 300mW/cm2, accumulative light quantity 300mJ/cm2Condition, from protective film (2) side irradiate ultraviolet light, make be bonded layers of polymer Solidification.So operating obtained laminated body has function as polarizer.
For obtained laminated body (polarizer), add according to the following method evaluation peel strength, gel fraction, punching Work, shrinking percentage, heat resistance and humidity resistance.The results are shown in Table 7 for it.
< peel strength >
Bonding force is according to JIS K6854-4 bonding agent-removing adhesive strength test method(s)-the 4: dance roller method carries out Measurement.That is, obtained polarizer is cut into 25mm × 150mm size as test sample using cutter.It is used in the measurement On the two sides of sample, across adhesive tape (the DF 8712S of TOYOCHEM company manufacture), attached using laminating machine (laminater) Metal plate obtains the measurement laminated body being made of polarizer and metal plate.In the measurement on laminated body (polarizer), Stripping portion is preset between protective film and polarizer.Under conditions of 23 DEG C, relative humidity 50%, with 300mm/ minutes Speed peels the measurement laminated body by above-mentioned stripping portion, and measures peeling force.At this point, the measurement of peeling force is to polyethylene It is implemented both between alcohol system polarizer and protective film (1) and between polyethenol series polarizer and protective film (2). Using the peeling force as bonding force, evaluated according to evaluation criteria below.It is actually to make if being evaluated as " C " or more With the grade of no problem.
(evaluation criteria)
A: not peelable or polarizer destroys
B: peeling force is 2.0 (N/25mm) more than and less than 5.0 (N/25mm).
C: peeling force is 1.0 (N/25mm) more than and less than 2.0 (N/25mm).
D: peeling force is less than 1.0 (N/25mm).
< gel fraction >
In polynorbornene mesentery (trade name " the ZEONOR ZF- for the Japanese ZEON company manufacture for not imposing sided corona treatment 14:100 μm ") on, using bar coater, the resin combination of each coordinating example is coated with as bonding agent, forms film thickness 20 to 25 μm polymerism adhesive layer.In addition, stacking does not impose the ZEONOR ZF-14 of sided corona treatment on above-mentioned polymerism adhesive layer, Obtain that there is hyaline membrane/adhesive layer/hyaline membrane 3-tier architecture laminated body to use active energy beam irradiation unit later (Toshiba's manufacture, high-pressure sodium lamp), with maximal illumination 300mW/cm2, accumulative light quantity 300mJ/cm2Condition, irradiate active energy Ray is measured, above-mentioned polymerism adhesive layer polymerizing curable is made.Then, it is removed respectively from the laminated body of obtained 3-tier architecture transparent Film (ZEONOR ZF-14), obtains adhesive layer.Adhesive layer is then clipped in by the weight (weight 1) for measuring the adhesive layer Between metal mesh and metal mesh, adhesive layer is maintained not to be laminated, reflux 3 hours in methyl ethyl ketone (MEK).Later, in 80 DEG C temperature under the conditions of after dry 30 minutes, measure the weight (weight 2) of adhesive layer.These values are used for following formula, to ask Gel fraction out.
Gel fraction (%)={ 1- (weight 1- weight 2)/weight 1 } × 100
In turn, it is evaluated according to evaluation criteria below.
(evaluation criteria)
A: gel fraction is 90% or more
B: gel fraction is 80% less than 90%
C: gel fraction is less than 80%
In addition, gel fraction indicates residual point of dissolution of resin relative to solvent, it is related to the crosslink density in polymerizing curable, For the simplified method for determining crosslink density, if gel fraction is low, then it represents that high to the dissolubility of solvent, crosslink density is low.Another party Face, if gel fraction is high, then it represents that low to the dissolubility of solvent, crosslink density is high.In above-mentioned evaluation criteria, if be evaluated as It is then the grade for actually using upper no problem more than " C ".
< punching processing >
It, will be inclined made by each embodiment and each comparative example using the knife for 100mm × 100mm that Dumbbell company manufactures Tabula rasa is from protective film (1) side punching.With the peel distance on the polarizer periphery of gage measurement punching, and according to evaluation base below Standard is evaluated.It is the grade for actually using upper no problem if being evaluated as " C " or more.
(evaluation criteria)
A:0mm
B:1mm or less
C:1 to 3mm
D:3mm or more
< shrinking percentage >
Above-mentioned polarizer small pieces are respectively placed in the constant temperature and humidity machine of 60 DEG C of-dry and 60 DEG C of -90RH%, measurement 60 The shrinkage of extending direction after hour, finds out shrinkage relative to the ratio of raw footage (100mm) as shrinking percentage.In addition, It is evaluated according to evaluation criteria below.In addition, so-called " dry ", is only to control temperature in the baking oven for having humidity adjustment function Degree, experimental condition when not controlling humidity.It is the grade for actually using upper no problem if being evaluated as " B " or more.
(evaluation criteria)
A: shrinking percentage is 0.2% or less
B: shrinkage ratio 0.2% is big and is 0.4% or less
C: shrinking percentage is more than 0.4%.
< heat resistance >
The obtained each polarizer of each embodiment C1 to C28, comparative example C1 to C4 is cut into 50mm × 40mm size, Under conditions of 80 DEG C of-dry and 100 DEG C of-dry, respectively expose to the open air 1000 hours.Polarizer end after judgement exposes to the open air by visual observation Whether there is or not removings.And then it is evaluated according to evaluation criteria below.It is that the upper nothing of actual use is asked if being evaluated as " C " or more The grade of topic.
(evaluation criteria)
A: entirely without removing under conditions of 100 DEG C of-dry.
B: entirely without removing under conditions of 80 DEG C of-dry.
C: there is the removing less than 1mm under conditions of 80 DEG C of-dry.
D: there is the removing of 1mm or more under conditions of 80 DEG C of-dry.
< humidity resistance >
The obtained each polarizer of each embodiment C1 to C28, comparative example C1 to C4 is cut into 50mm × 40mm size, It is exposed to the open air 1000 hours under conditions of 60 DEG C of -90%RH and under conditions of 85 DEG C of -85%RH.Judgement, which exposes to the open air, by visual observation retrodeviates Whether there is or not removings for tabula rasa end.And then it is evaluated according to evaluation criteria below.It is actually to make if being evaluated as " C " or more With the grade of no problem.
(evaluation criteria)
A: entirely without removing under conditions of 85 DEG C of -85%RH.
B: entirely without removing under conditions of 60 DEG C of -90%RH.
C: there is the removing less than 1mm under conditions of 60 DEG C of -90%RH.
D: there is the removing of 1mm or more under conditions of 60 DEG C of -90%RH.
[table 7]
The detail for the optical film recorded in table 7 is as follows.
ZF-14: the polynorbornene mesentery of Japanese ZEON company manufacture.
HBD-002: the polyacrylic acid mesentery of Mitsubishi's Li Yang company manufacture.
(embodiment D1 to D31 and Comparative Example D 1 to D4)
Use resin combination shown in table 5 and 6 as active energy beam polymerism smears, following to operate, manufacture With optical film/coating oxidant layer structure laminated body.In above-mentioned laminated body, as optical film, manufactured using Fuji Photo Film Co., Ltd. The poly- tri acetyl cellulose mesentery containing ultraviolet absorbing agent: trade name " FUJITAC:80 μm ".Firstly, to the optical film table Face, with 300Wmin/m2Discharge capacity carry out sided corona treatment.After managing at the surface within 1 hour, using bar coater, It is coated with the resin combination of each coordinating example on the surface of the film, forms 4 μm of film thickness of polymerism and is coated with oxidant layer.
Then, in such a way that optical film is connected to terneplate, the four directions of above-mentioned laminated body is consolidated with celo sweet smell adhesive tape It is scheduled on terneplate.Then, it will be replaced in UV irradiation unit (Toshiba manufactures, high-pressure sodium lamp) with dry nitrogen Afterwards, with the maximal illumination 300mW/cm of wavelength 365nm2, accumulative light quantity 300mJ/cm2Condition, from above-mentioned polymerism smears Ultraviolet light is irradiated in layer side, makes its polymerizing curable, obtains the laminated body with coating oxidant layer.To so operating obtained stacking Body finds out closing force, heat resistance according to the following method.The results are shown in Table 8 for it.
< closing force >
Implement gridiron pattern disbonded test according to JIS K5400.By the block number removed in 100 pieces, according to evaluation base below Standard is evaluated.It is the grade for actually using upper no problem if being evaluated as " C " or more.
(evaluation criteria)
A:0 block
B:1 to 10 pieces
C:11 to 30 pieces
It is more than D:31 block
< heat resistance >
Embodiment D1 to D31 and Comparative Example D 1 to the obtained laminated body of D4 are cut into 50mm × 40mm size, in 80 It is exposed to the open air 1000 hours under conditions of DEG C-dry.Judgement exposes rear laminated body end to the open air whether there is or not removings by visual observation.And then according to following Evaluation criteria evaluated.It is the grade for actually using upper no problem if being evaluated as " B " or more.
(evaluation criteria)
A: entirely without removing.
B: there is the removing less than 1mm.
C: there is the removing of 1mm or more.
[table 8]
The details for the optical film recorded in table 8 are shaped like under.
FUJITAC: Fuji Photo Film Co., Ltd.'s manufacture, the TAC mesentery (80 μm) containing ultraviolet absorbing agent.
ZF-14: Japanese ZEON company manufacture, the polynorbornene mesentery (100 μm) without ultraviolet absorbing agent.
HBD-002: the manufacture of Mitsubishi's Li Yang company, the polyacrylic acid mesentery (50 μm) without ultraviolet absorbing agent.
The manufacture of R-140:Kaneka company, the polycarbonate mesentery (43 μm) without ultraviolet absorbing agent.
The manufacture of Emblet S:Unitika company, the polyester mesentery (50 μm) containing ultraviolet absorbing agent.
The manufacture of TUX-HZ:Tohcello company, the polyethylene mesentery (50 μm) containing ultraviolet absorbing agent.
In the present invention, it is not limited to above-mentioned optical film, it is excellent to constitute various characteristics aspect that various optical films can be used Laminated body.
When as above using resin combination of the invention as active energy beam polymerism bonding agent, as shown in table 7, In embodiment C1 into C28, though viscosity has a little high, special problem is had no, excellent layer in terms of various characteristics can be formed Stack.In contrast, in comparative example C1 into C4, it is known that especially bonding force reduces, in terms of punching processing, shrinking percentage Difference.In addition, being also shown and 7 institute of table when using resin combination of the invention as active energy beam polymerism smears The result shown similarly is inclined to.That is, as shown in table 8, for embodiment D1 into D31, closing force and heat resistance are excellent, can be without spy Other problem ground forming layer stack.In contrast, in Comparative Example D 1 into D4, it is known that lack closing force and heat resistance, especially its In either it is all particularly poor.

Claims (11)

1. a kind of resin combination for as the bonding agent or smears for constituting optical laminated body, is that active-energy is penetrated Line polymer resin composition, it includes:
Intramolecular at least has 1 or more α, the oligomer (A) that β-unsaturated double-bond base and weight average molecular weight are 300 to 50,000 1 to 99.8 parts by weight,
Intramolecular has 1 or more carboxyl and acid value is 100 to 1,000mg KOH/g containing α, β-unsaturated double-bond base chemical combination 0.1 to 49.5 parts by weight of object monomer (B) and
0.1 to 49.5 parts by weight of cyclic imines (C1) or carbodiimide compound (C2),
The cyclic imines (C1) are the compound that intramolecular has 1 or more the aziridine ring for having 3 ring structures,
The carbodiimide compound (C2) is the compound that intramolecular has 1 or more carbodiimide key base,
Described it will contain α, β-unsaturated double-bond base compound monomer (B) and the cyclic imines (C1) or the carbon two When the total weight of group with imine moiety (C2) is set as 100 weight %, the cyclic imines (C1) or the carbodiimide The ratio of compound (C2) is the range of 20 to 80 weight %.
2. resin combination as described in claim 1, wherein the oligomer (A) includes to be selected from Polyester oligomer (a- 1), in group composed by polyurethane series oligomer (a-2), poly- epoxy oligomer (a-3) and polyacrylic oligomer (a-4) At least one or more oligomer.
3. resin combination as claimed in claim 1 or 2, wherein the weight average molecular weight of the oligomer (A) is 300 to 30, 000。
4. resin combination as claimed in claim 1 or 2, further contains: intramolecular contains α without carboxyl, and β-is no It is saturated the compound monomer (D) of double bond base.
5. resin combination as claimed in claim 1 or 2 further contains active energy beam polymerization initiator (E), and The use level of the active energy beam polymerization initiator (E) relative to resin combination 100 parts by weight of total amount 0.01 to 20 parts by weight ranges.
6. resin combination as claimed in claim 1 or 2 further contains silane compound (F).
7. resin combination as claimed in claim 1 or 2 is that active energy beam polymerism smears or active-energy are penetrated Line polymerism bonding agent.
8. a kind of optical laminated body, include substrate and be arranged on an at least interarea for the substrate by claim 1 The resin layer constituted to resin combination described in 7 wantonly 1.
9. optical laminated body as claimed in claim 8, wherein the substrate is hyaline membrane.
10. optical laminated body as claimed in claim 9, wherein the hyaline membrane be selected from poly- acetylcellulose mesentery, Polynorbornene mesentery, polypropylene mesentery, polyacrylic acid mesentery, polycarbonate mesentery, polyester mesentery, polyvinyl alcohol mesentery and It is at least one kind of in group composed by polyimides mesentery.
11. a kind of optical laminated body, include optical film and be arranged on an at least interarea for the optical film by right It is required that the resin layer that resin combination described in wantonly 1 is constituted in 1 to 7.
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