CN106459322A - Active energy ray curable resin composition, cured product thereof and molded product thereof - Google Patents
Active energy ray curable resin composition, cured product thereof and molded product thereof Download PDFInfo
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- CN106459322A CN106459322A CN201580030336.5A CN201580030336A CN106459322A CN 106459322 A CN106459322 A CN 106459322A CN 201580030336 A CN201580030336 A CN 201580030336A CN 106459322 A CN106459322 A CN 106459322A
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- energy ray
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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
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromonomer-Based Addition Polymer (AREA)
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Abstract
Provided is an active energy ray curable resin composition that exhibits excellent chemical resistance and has high hardness, while exhibiting a low amount of warping and superior adhesiveness to a film substrate. Also provided are a cured product and a molded product of said active energy ray curable resin. The active energy ray curable resin composition contains: a bifunctional urethane (meth)acrylate oligomer having a polyester skeleton; an acrylamide and/or a derivative thereof; and a monofunctional (meth)acrylate monomer having a heterocyclic group.
Description
Technical field
The present invention relates to curable with actinic energy ray resin combination, hardened obtained by hardening thing and formed body,
Described energy line hardened resin composition is just rapid curing by the irradiation of the active energy ray of ultraviolet etc., it is adaptable to manufacture
The hardening thing that chemical reagent resistance is good, warpage properties is low, hardness is high and the adherence of base material is excellent.
Background technology
In recent years, with information terminals such as the portable communication device such as mobile phone or smart mobile phone, panel computer, vehicle-mounted
The slimming of stereo set etc. and lightweight, input block, decorative element that these equipment are had also receive slimming
Require for example there are the need by thin module obtained by one-body molded simply for animi resin on the base materials such as the film with flexibility
Ask.
It even if these parts are thin module, is also required to there is patience to the impact such as falling, even if Long-Time Service is not yet
Have a change of tone, shape, physical property, and also very reliable under hot and humid environment, and when they are as outside outermost
It during dress parts, is also requested to have mar proof, marresistance.
The hardening thing being obtained by curable with actinic energy ray resin combination due to have chemical reagent resistance, high rigidity,
It is known with the excellent specific property of the adherence of base material, obdurability etc., owing to it can by active energy ray at short notice
Hardening, the transparency is also excellent, is therefore the material of the hard material suitably functioning as above-mentioned thin module.As this active energy ray
Hardened resin composition, for example, has recorded in Japanese Unexamined Patent Publication 2011-173982 publication (patent document 1) and has not contained to have
The bifunctional acrylate of the cyclic skeleton of double bond is as raw-material example.
Prior art literature
Patent document
Patent document 1:Japanese Unexamined Patent Publication 2011-173982
Content of the invention
Problems to be solved by the invention
This curable with actinic energy ray resin combination can be carried by using the bifunctional acrylate with cyclic skeleton
High crosslink density, thus obtain excellent effect at the aspect such as case hardness, mar proof.But, due to difunctional acrylate
The addition of ester will not have effect less, if therefore adding enough amounts, then contraction when hardening becomes big, once with film etc.
Base material integrated molding and when obtaining product, then have warpage and become big, the fretful problem of base material.
It is not limited only to such example, the research discovery according to the present inventor, case hardness or chemical reagent resistance etc.
Characteristic, and, the characteristic such as warpage properties when one-body molded with the base material of film etc. or the adherence with base material, they are deposited each other
At tradeoff, adjust crosslink density by increase and decrease bifunctional acrylate and be difficult to all meet these characteristics.
Therefore, the present invention completes to solve such problem, its object is to provide chemical reagent resistance excellent
Different, not only hardness is high but also warpage is few and the adherence of base material is excellent curable with actinic energy ray resin combination, its hardening
Thing and formed body.
For solving the method for problem
The present invention is to solve that the problems referred to above constitute as follows.
Curable with actinic energy ray resin combination, it contains：Possesses difunctional urethane's (methyl) third of polyester backbone
Olefin(e) acid ester oligomer, select from acrylamide or derivatives thereof one of at least any and the simple function (first possessing heterocyclic radical
Base) acrylate monomer.
Owing to containing difunctional urethane's (methyl) acrylate oligomer possessing polyester backbone, thus available strong
Tough hardening thing, and owing to containing select from acrylamide or derivatives thereof one of at least any, thus can improve with
The adherence of the base materials such as the film that resin or rubber are made.Further, since contain simple function (methyl) propylene possessing heterocyclic radical
Acid ester monomer, thus while maintaining low curing shrinkage rate, the case hardness of hardening thing can be improved, and its chemically-resistant can be given
Agents.
As simple function (methyl) acrylate monomer possessing heterocyclic radical, tetrahydrofuran base (methyl) acrylic acid can be enumerated
Ester, trimethylolpropane formal (methyl) acrylate.
The element of the ring constituting heterocyclic radical can simply be carbon and oxygen.The element of ring owing to constituting heterocyclic radical be only carbon and
Oxygen, it is possible to obtain the effect of the oxygen-containing raising chemical reagent resistance bringing or bring based on oxygen containing soft skeleton
Obdurability.On the contrary, when containing element beyond oxygen, have and cannot fully obtain the obdurability of hardening thing or adhesive feelings
Condition.
Such heterocyclic radical can be oxirane ring, ortho-xylene ring, oxetanes ring, tetrahydrofuran ring, two
One of at least any in oxygen pentane ring, oxane ring or dioxanes ring.
And then, the present invention provide hardening thing that above-mentioned curable with actinic energy ray resin combination is polymerized and
Formed body obtained by this hardening thing one-body molded on base material.
Owing to being the hardening thing making above-mentioned curable with actinic energy ray resin combination harden, therefore not only have resistance to
Chemical agents, high rigidity, and warpage is few, also excellent with the adherence of base material.With the base material of film etc. one-body molded obtained by
Formed body is also such.
Make hardening thing that curable with actinic energy ray resin combination hardens as with active energy ray and at base material
Formed body obtained by upper this hardening thing one-body molded, can enumerate keypad or pressing pieces, decoration molded component etc..
As keypad, e.g. there is substrate, the key top film being formed at the substantially whole face of this substrate surface and this key
The keypad of the prominent key top main body that teleblem is locally thicker, or there is the key top of the local surfaces being formed at substrate
The keypad of main body, described key top film and described key top main body are obtained by curable with actinic energy ray resin combination hardens
Hardening thing is constituted.
As substrate, in addition to resin film, sheet rubber, sheet metal etc., also can enumerate by thermoplastic resin or rubber
The slim formed products constituting.
Invention effect
Curable with actinic energy ray resin combination according to the present invention, can produce and have chemical reagent resistance, warpage
Property low, hardness is high and the adherence of base material is excellent hardening thing, and according to the hardening thing of the present invention and formed body, so that it may tool
Standby such character.
Detailed description of the invention
Illustrate that the present invention is elaborated by embodiment.Curable with actinic energy ray resin combination described below
At least contain：Possess polyester backbone difunctional urethane's (methyl) acrylate oligomer (composition A), from acrylamide and its
One of at least any (composition B) and simple function (methyl) acrylate monomer (composition possessing heterocyclic radical selected in derivative
C).
Difunctional urethane's (methyl) acrylate oligomer possessing polyester backbone is Difunctional oligomers.Use double official
The reason that energy being, if more than trifunctional, then crosslink density can become too high.If an in addition, only sense (single official
Can) oligomer, just cannot grow three-dimensional crosslinking structure, thus tough hardening thing cannot be obtained.In addition, the weight of this oligomer
Average molecular weight is preferably 1, and 000～20,000.If less than 1,000, then crosslink density becomes too high, it is possible to have hardening thing
Warpage become big problem.In addition, if it exceeds 20,000, then viscosity can become excessive, thus the change easy to manufacture of formed body
Difficult.
As such difunctional urethane (methyl) acrylate oligomer, available Toagosei Co., Ltd, sand
The various products that Duo Ma company or Kyoeisha Chemical Co., Ltd. etc. manufacture, such difunctional urethane (methyl) acrylate
Oligomer can be used alone, it is also possible to mixes two or more use.
The glass transition temperature (Tg) of difunctional urethane's (methyl) acrylate oligomer possessing polyester backbone is excellent
Elect-30 DEG C～60 DEG C as, more preferably 20 DEG C～55 DEG C.So, it is readily obtained base material adherence, low warpage properties, high rigidity, resistance to
The hardening thing that chemical agents has both.If Tg is less than-30 DEG C, although then low warpage properties is good, but hardness, chemical reagent resistance
Have the tendency of variation, and if Tg is more than 60 DEG C, then low warpage properties has the tendency of variation.
As acrylamide or derivatives thereof, (methyl) acrylamide, N-methyl (methyl) acrylamide, N, N-can be enumerated
Dimethyl (methyl) acrylamide, N-n-propyl (methyl) acrylamide, N-isopropyl (methyl) acrylamide, N, N-diethyl
(methyl) acrylamide, N-methyl-N-n-propyl (methyl) acrylamide, N-methyl-N-isopropyl (methyl) acrylamide, N-
Ethoxypropyl (methyl) acrylamide, N-tetrahydrofurfuryl (methyl) acrylamide, N-ethoxyethyl group (methyl) acrylamide, N-
1-methyl-2-methoxyethyl (methyl) acrylamide, N-morpholine propyl group (methyl) acrylamide, N-methoxy-propyl (methyl) third
Acrylamide, N-isopropoxyethyl (methyl) acrylamide, N-isopropyl oxygen propyl group (methyl) acrylamide, N-hydroxymethyl (methyl)
The aliphatic propylene of acrylamide, N-(2-ethoxy) (methyl) acrylamide, N-(3-hydroxypropyl) (methyl) acrylamide etc.
Acid amides or derivatives thereof, N-caprolactam, NVP, N-(methyl) acryloyl morpholine, N-(methyl)
Cyclic acrylamides of Antiepilepsirin etc. or derivatives thereof.Preferably there is the acrylamide of (methyl) acryloyl group or it derives
Thing, and N-acryloyl morpholine is one of particularly preferred acrylamide or derivatives thereof.
The addition of acrylamide or derivatives thereof is preferably 3～40 weight % relative to solid constituent total amount, more preferably
It is 5～20 weight %.If addition is less than 3 weight %, then there is variation with the adherence of base material, if addition is big
In 40%, then the adherence and between casting mould uprises, and demolding performace has the tendency of variation.
Possess simple function (methyl) acrylate monomer of heterocyclic radical by containing acrylamide or derivatives thereof, it is thus possible to
While maintaining low curing shrinkage rate, the hardness of hardening thing can be improved, and its chemical reagent resistance can be given.
As simple function (methyl) acrylate monomer possessing heterocyclic radical, for example, can enumerate tetrahydrofuran base (methyl) third
Olefin(e) acid ester, cyclic trimethylolpropane formal (methyl) acrylate, pentamethvl base (methyl) acrylate, tetramethyl
Piperidyl (methyl) acrylate, (methyl) acryloyl morpholine etc..
Agents owing to can obtain high resistance to chemicals because of oxygen-containing in heterocyclic radical, the element of the ring therefore constituting heterocyclic radical is only
Carbon and oxygen are one of preferred embodiment.As such heterocycle, oxirane ring, ortho-xylene ring, oxa-ring can be enumerated
Butane ring, tetrahydrofuran ring, dioxolane ring, oxane ring, dioxanes ring etc..Oxygen containing simple function (methyl) third in heterocyclic radical
Among alkene acid ester monomer, from the perspective of giving extra high chemical reagent resistance, preferably tetrahydrofuran base (methyl) third
Olefin(e) acid ester or trimethylolpropane formal (methyl) acrylate.
It is preferably mixed together ring-type single official of non-heterocyclic radical with simple function (methyl) acrylate monomer possessing heterocyclic radical
The form of energy (methyl) acrylate monomer.So, when simple function (methyl) acrylate monomer possessing heterocyclic radical in minimizing
Content when, if ring-type simple function (methyl) acrylate monomer mixing such non-heterocyclic radical helps to improve resistance toization
Learn agents, hardness.As an example of ring-type simple function (methyl) acrylate monomer, the different ice of methacrylic acid can be enumerated
Piece ester or cyclohexyl methacrylate etc..
Possess simple function (methyl) acrylate monomer of heterocyclic radical and ring-type simple function (methyl) acrylate monomer
Total content is preferably 35～55 weight % relative to solid constituent total amount.If fewer than 35 weight %, then there may be hardness fall
The problem that low, chemical reagent resistance is deteriorated.In addition, if it exceeds 55 weight %, then difunctional urethane's (methyl) acrylate
The content of oligomer is just relative to be reduced, and the obdurability having a hardening thing is impaired and the tendency that becomes fragile.
As Photoepolymerizationinitiater initiater, Benzophenone class, thioxanthene ketone, acetophenone class, acylphosphanes class etc. can be used, for example, can lift
Go out the IRGACURE (trade name) etc. that BASF Japanese firm manufactures, and a kind of Photoepolymerizationinitiater initiater can be used, it is possible to combination makes
With two or more Photoepolymerizationinitiater initiaters.The addition of Photoepolymerizationinitiater initiater is relative to difunctional urethane's (first of 100 weight portions
Base) acrylate oligomer, preferably 0.1～10 weight portion, more preferably 0.3～5 weight portion.
Various diluent, additive, packing material etc. can be added according to various purposes in such composition.As it
In a case, as long as containing the inorganic filling material of amorphous silicon oxide or calcium carbonate etc., so that it may improve hardening thing mechanical strength,
The characteristics such as chemical reagent resistance.As long as in addition, contain the colouring agents such as phthalocyanine blue, titanium oxide or carbon black, so that it may hardening thing is carried out
Coloring.
The viscosity of curable with actinic energy ray resin combination is preferably 150～1500mPa s when 25 DEG C.If it is viscous
Degree is less than 150mPa s, then, during die casting, material can flow out and forming difficulty, if viscosity is higher than 1500mPa s, then difficult
With casting, it is difficult to obtain the formed products of intended shape.
Curable with actinic energy ray resin combination can be used for being coated on the base material being made up of resin or elastomer etc., or
Adhere with these base materials after injecting mould.
As the active energy ray for making curable with actinic energy ray resin combination harden, except ultraviolet, also may be used
Enumerate electron beam, visible ray, infrared light, X-ray, alpha ray, β ray, gamma-rays etc., as launching these active energy rays
Light source, UV light source or UV-LED light source, various mercury vapor lamp or sodium vapor lamp, xenon lamp, metal halide lamp etc. can be enumerated.
Embodiment
The manufacture of curable with actinic energy ray resin combination：
Preparation is containing as the composition A of difunctional urethane's acrylate oligomer with polyester backbone, as propylene
The composition B of acid amides or derivatives thereof and the activity of the composition C as simple function (methyl) acrylate monomer possessing heterocyclic radical
Energy line hardened resin composition, and prepare the curable with actinic energy ray resin wherein lacking a part of mentioned component
Composition, produces sample 1～sample 10 respectively.The details of the composition constituting each composition be shown in table 1 below and
In table 2.
Table 1
Table 2
Mark in table 1 and table 2 is as follows.
·CN9009：The trade name that Sartomer produces.There is difunctional urethane's acrylate of polyesters bone lattice
Oligomer.
·CN9788：The trade name that Sartomer produces.There is difunctional urethane's acrylate of polyesters bone lattice
Oligomer.
·CN996：The trade name that Sartomer produces.Difunctional urethane's acrylate with polyethers bone lattice is low
Polymers.
·CN929：The trade name that Sartomer produces.The trifunctional urethane acrylate with polyesters bone lattice is low
Polymers.
·IRGACURE184：The trade name that BASF Japanese firm produces.
Each active energy ray hardening to the sample 1～sample 10 formulated by the mixed proportion shown in table 1 and table 2
Type resin combination, tests and have evaluated their base material adherence, warpage properties, hardness, curing shrinkage rate, resistance to using the following method
Chemical agents, demolding performace.Its result is also depicted in table 1.
Base material adherence：
Test the adherence between base material when making each sample be hardened on the resin constituting base material and hardening thing.
Prepare the easily adhesion PET of thick 300 μm as base material, sample is filled to diameter 5mm, high 5mm size can be obtained
In the mould of hardening thing, in the way of not admitting air into, cover easily adhesion PET on its surface, and with illuminance：500mW/
cm2, accumulated light：3000mJ/cm2Condition, above easy adhesion PET, irradiate active energy ray (ultraviolet), make sample solid
Change, carry out the demoulding.
With regard to adherence, the end being fixed with the easily hardening thing of adhesion PET on the surface of diameter 5mm hangs up hook, it is determined that
Stripping difficulty during strip hardened thing.By the unstripped "○" that is evaluated as, what difficulty was peeled off is evaluated as " △ ", and be easily peeled off comments
Estimate for "×".
Warpage properties：
Make each sample shape in a thin-layered way and harden and obtain hardening thing, testing the warpage degree of this hardening thing.
Prepare identical with base material viscosity test easily adhesion PET, sample is filled to can obtain 120mm × 45mm ×
In the mould of the hardening thing of 0.3mm size, in the way of not admitting air into, cover easily adhesion PET on its surface, and with illumination
Degree：500mW/cm2, accumulated light：3000mJ/cm2Condition, irradiation ultraviolet radiation above easy adhesion PET.After the demoulding, at 80 DEG C
Place under environment 1 hour, at room temperature cool down 30 minutes.And then, measure amount of warpage maximum in hardening thing with height-gauge
Part, illustrates the length (mm) of this warpage.
Hardness：
Produce the hardening thing being fixed on base material identically with base material viscosity test, based on JIS K7215, Xiao will be measured
The hardometer of family name's hardness D shelves is without impact and promptly presses on hardening thing, measures the maximum of hardening thing now.
Curing shrinkage rate：
Proportion after proportion according to said sample and the hardening of this sample, obtains curing shrinkage rate.According to JIS Z8807,
And by measuring the proportion of presclerotic sample by the density of specific gravity bottle and gravity test method, according to JIS Z8807,
And by measuring the proportion of hardening thing by the density of weighing method in water and hydrometry, and then asked by following formula
Go out curing shrinkage rate.
Curing shrinkage rate (%)=[(proportion after hardening)-(proportion before hardening)]/(proportion after hardening) × 100
Chemical reagent resistance：
At 500mW/cm2, accumulated light：3000mJ/cm2Under conditions of, irradiate each sample with ultraviolet, produce 10mm
The hardening thing of × 50mm × 0.5mm size.This hardening thing is immersed in two kinds of chemical reagent, according to obtained by following formula
Swellbility assesses chemical reagent resistance.
Swellbility=in chemical reagent impregnate after weight/impregnate in chemical reagent before weight
As chemical reagent, prepare oleic acid and ethanol, impregnate 24 hours in oleic acid with 50 DEG C respectively, with 25 DEG C at ethanol
Middle dipping 24 hours.
Demolding performace：
Sample is filled to the mould of the recess with multiple 10mm × 5mm × deep 0.5mm, cover above-mentioned easy adhesion
Whether PET, after irradiation ultraviolet radiation makes sample solidification under these conditions, test and be easily removed from the molds.
It in the judgement of demolding performace, is designated as "○" by be easily removed from the molds, will be not easily taken out of and be designated as "×".
Make the assessment of the hardening thing that curable with actinic energy ray resin combination hardens：
Containing possess difunctional urethane's (methyl) acrylate oligomer (composition A) of polyester backbone, acrylamide or
Its derivative (composition B) and possess heterocyclic radical simple function (methyl) acrylate monomer (composition C) sample 1～sample the 5th,
The curable with actinic energy ray resin combination of sample 9 is good in complete characteristic assessment.
On the other hand, employ and possess difunctional urethane's (methyl) acrylate oligomer of polyethers bone lattice and replace tool
The sample 8 of difunctional urethane's (methyl) acrylate oligomer (composition A) of standby polyester backbone, its hardness is 58, and ethanol is molten
Expansibility is 1.21, occurs in that the result of hardness deficiency and chemical reagent resistance difference.In addition, have employed three officials of identical polyester backbone
Difunctional urethane's (methyl) acrylate possessing polyester backbone can be replaced low by polyurethane (methyl) acrylate oligomer
The sample 10 of polymers (composition A), its warpage properties increases to 7.2mm, and result is that warpage becomes problem.
In addition, be not added with the sample 6 of the acryloyl morpholine as acrylamide or derivatives thereof (composition B), its hardness is low
To 52, in addition, base material adherence is also not so good.And, do not contain simple function (methyl) acrylate monomer (one-tenth possessing heterocyclic radical
Point C) sample 7, its oleic acid swellbility is 1.16, and ethanol swellbility is 1.18, chemical reagent resistance difference.
Claims (6)
1. curable with actinic energy ray resin combination, it is characterised in that containing the difunctional urethane's (first possessing polyester backbone
Base) acrylate oligomer, select from acrylamide or derivatives thereof one of at least any and the single official possessing heterocyclic radical
Can (methyl) acrylate monomer.
2. curable with actinic energy ray resin combination as claimed in claim 1, it is characterised in that constitute described heterocyclic radical
The element of ring is only carbon and oxygen.
3. curable with actinic energy ray resin combination as claimed in claim 1 or 2, it is characterised in that described heterocyclic radical is
In oxirane ring, ortho-xylene ring, oxetanes ring, tetrahydrofuran ring, dioxolane ring, oxane ring or dioxanes ring
One of at least any.
4. the curable with actinic energy ray resin combination as according to any one of claims 1 to 3, it is characterised in that described
Simple function (methyl) acrylate monomer comprises tetrahydrofuran base (methyl) acrylate or trimethylolpropane formal (first
Base) one of at least any in acrylate.
5. hardening thing, it is characterised in that make the active energy ray according to any one of Claims 1 to 4 hard with active energy ray
The hardening of change type resin combination forms.
6. formed body, it is characterised in that make the hardening thing described in claim 5 one-body molded on base material and formed.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014125322 | 2014-06-18 | ||
| JP2014-125322 | 2014-06-18 | ||
| PCT/JP2015/067091 WO2015194487A1 (en) | 2014-06-18 | 2015-06-12 | Active energy ray curable resin composition, cured product thereof and molded product thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106459322A true CN106459322A (en) | 2017-02-22 |
Family
ID=54935474
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580030336.5A Pending CN106459322A (en) | 2014-06-18 | 2015-06-12 | Active energy ray curable resin composition, cured product thereof and molded product thereof |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPWO2015194487A1 (en) |
| CN (1) | CN106459322A (en) |
| WO (1) | WO2015194487A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110437385A (en) * | 2019-07-09 | 2019-11-12 | 湖南昇微新材料有限公司 | A kind of 3D printing photochromic material and preparation method thereof and its application method |
| CN110437376A (en) * | 2019-07-09 | 2019-11-12 | 湖南昇微新材料有限公司 | High-precision 3D printing thermochromic material and preparation method thereof and its application method |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7541011B2 (en) | 2018-09-24 | 2024-08-27 | ビーエーエスエフ ソシエタス・ヨーロピア | Photocurable compositions for use in 3D printing |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63117023A (en) * | 1986-11-05 | 1988-05-21 | Nippon Kayaku Co Ltd | Resin composition and printing ink composition |
| JPH10130586A (en) * | 1996-10-30 | 1998-05-19 | Nippon Kayaku Co Ltd | Adhesive composition, cured material, article and bonding |
| JP2003268026A (en) * | 2002-03-12 | 2003-09-25 | Teikoku Printing Inks Mfg Co Ltd | Ultraviolet light-curing composition, ultraviolet light- curing ink and printed material |
| JP2005255844A (en) * | 2004-03-11 | 2005-09-22 | Jsr Corp | Radiation curable composition |
| JP2011256307A (en) * | 2010-06-10 | 2011-12-22 | Mitsubishi Rayon Co Ltd | Active energy ray-curable resin composition for casting, and optical component |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3835857B2 (en) * | 1996-06-18 | 2006-10-18 | 日本化薬株式会社 | Adhesive composition for optical disk, cured product, article, and adhesion method |
| JP6308774B2 (en) * | 2012-12-28 | 2018-04-11 | 日本合成化学工業株式会社 | Active energy ray-curable resin composition and coating agent |
-
2015
- 2015-06-12 JP JP2016529318A patent/JPWO2015194487A1/en active Pending
- 2015-06-12 WO PCT/JP2015/067091 patent/WO2015194487A1/en active Application Filing
- 2015-06-12 CN CN201580030336.5A patent/CN106459322A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63117023A (en) * | 1986-11-05 | 1988-05-21 | Nippon Kayaku Co Ltd | Resin composition and printing ink composition |
| JPH10130586A (en) * | 1996-10-30 | 1998-05-19 | Nippon Kayaku Co Ltd | Adhesive composition, cured material, article and bonding |
| JP2003268026A (en) * | 2002-03-12 | 2003-09-25 | Teikoku Printing Inks Mfg Co Ltd | Ultraviolet light-curing composition, ultraviolet light- curing ink and printed material |
| JP2005255844A (en) * | 2004-03-11 | 2005-09-22 | Jsr Corp | Radiation curable composition |
| JP2011256307A (en) * | 2010-06-10 | 2011-12-22 | Mitsubishi Rayon Co Ltd | Active energy ray-curable resin composition for casting, and optical component |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110437385A (en) * | 2019-07-09 | 2019-11-12 | 湖南昇微新材料有限公司 | A kind of 3D printing photochromic material and preparation method thereof and its application method |
| CN110437376A (en) * | 2019-07-09 | 2019-11-12 | 湖南昇微新材料有限公司 | High-precision 3D printing thermochromic material and preparation method thereof and its application method |
| CN110437385B (en) * | 2019-07-09 | 2022-04-22 | 湖南昇微新材料有限公司 | Photochromic material for 3D printing and preparation method and application method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2015194487A1 (en) | 2015-12-23 |
| JPWO2015194487A1 (en) | 2017-05-25 |
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