CN110079196A - The manufacturing method of Photocurable composition and electronic component - Google Patents
The manufacturing method of Photocurable composition and electronic component Download PDFInfo
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- CN110079196A CN110079196A CN201811561851.8A CN201811561851A CN110079196A CN 110079196 A CN110079196 A CN 110079196A CN 201811561851 A CN201811561851 A CN 201811561851A CN 110079196 A CN110079196 A CN 110079196A
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- weight
- photocurable composition
- methyl
- photocurable
- acrylate
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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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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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
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- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
- Paints Or Removers (AREA)
- Materials For Photolithography (AREA)
- Polymerisation Methods In General (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The present invention provides a kind of Photocurable composition, and cured film can be improved relative to the adaptation for being coated with object Part, and due to being white, so as to improve the light reflectivity of cured film, and the heat resistance of cured film can be improved.Photocurable composition of the invention is used to partly and at multiple positions be coated on the surface in coating object Part, the Photocurable composition includes: epoxy (methyl) acrylate, has 2000 or more weight average molecular weight and does not have carboxyl；Photocurable compound, at least one ethylenic unsaturated bond and without 2000 or more weight average molecular weight, the photocurable compound is not epoxy (methyl) acrylate of the weight average molecular weight with 2000 or more；White pigment；Photoepolymerizationinitiater initiater, the content of epoxy (methyl) acrylate are 5 weight % or more and 30 weight % or less.
Description
The application is that application No. is 201580003223.6, entitled " Photocurable composition and the ministrys of electronics industry for China
The manufacturing method of part " and the applying date are the divisional application of the patent application on July 3rd, 2015.
Technical field
The present invention relates to the photo-curables partly and in the coating of multiple positions used on the surface of coating object Part
Composition.Moreover, it relates to the manufacturing method of the electronic component using above-mentioned Photocurable composition.
Background technique
As the protective film for protecting printed wiring board not influenced by high temperature scolding tin, welding resist film is widely used.
In addition, in various electronic components, the upper surface of printed wiring board equipped with light emitting diode (hereinafter referred to as
LED) chip.In order to print cloth sometimes using the light for the upper surface side for reaching above-mentioned printed wiring board from the light that LED is issued
The upper surface of line plate is formed with white welding resist film.White welding resist film contains white pigment.It is this white being formed
In the case that color welds resist film, not merely with the opposite side direct irradiation from the surface of LED chip to printed wiring board
Light, but also can use the reflected light for reaching the upper surface side of printed wiring board and being reflected by white resist film.Therefore, energy
Enough utilization efficiency improved by the LED light generated.
In addition, in addition to resist film purposes, in light reflection with using the cured film containing white pigment sometimes on the way.
As an example of the material for being used to form above-mentioned white resist film, one is disclosed in following patent documents 1
Kind anticorrosive additive material contains the silicon containing alkoxy obtained by the dealcoholization of epoxy resin and water-disintegrable alkoxy silane
Alkane modified epoxy, and it is also closely sealed containing the polycarboxylic acid resin containing unsaturated group, diluent, Photoepolymerizationinitiater initiater, solidification
Property imparting agent.
A kind of white solder mask material is disclosed in following patent documents 2, is contained without the carboxylic of aromatic rings
Resin, Photoepolymerizationinitiater initiater, epoxide, Titanium Dioxide Rutile Top grade, diluent.
A kind of be used to form is disclosed in following patent documents 3 to weld containing two layers of LED of white ink layer and priming coat
Connect the composition of resist film.The composition for being used to form above-mentioned white ink layer contains: (A1) polyurethane acrylate resin
Or mixture, that is, photopolymerization reaction polymer of polyurethane acrylate resin and Epocryl, (A2) relative to
The white pigment and (A3) that above-mentioned 100 mass parts of photopolymerization reaction polymer (A1) are 100~170 mass parts are relative to upper
State the Photoepolymerizationinitiater initiater that 100 mass parts of photopolymerization reaction polymer (A1) are 10~50 mass parts.It is used to form above-mentioned bottom
The composition of coating contains: (B1) is as the photopolymerization reaction polymer of Epocryl, (B2) relative to above-mentioned
The filler and (B3) that 100 mass parts of photopolymerization reaction polymer (B1) are 200~300 mass parts are relative to above-mentioned light
100 mass parts of polymerisation reactivity polymer (B1) are the Photoepolymerizationinitiater initiater of 10~50 mass parts.
Existing technical literature
Patent document
Patent document 1:(Japan) special open 2007-249148 bulletin
Patent document 2:(Japan) special open 2007-322546 bulletin
Patent document 3:(Japan) special open 2013-194057 bulletin
Summary of the invention
Technical problems to be solved by the inivention
In the material that patent document 1,2 is recorded, in order to form resist film, the exposure process and development work in photoetching are needed
Multiple processes such as sequence.Therefore, process number increases, and the manufacture efficiency of electronic component etc. is poor.
Moreover, in the material that patent document 1,2 is recorded, due to using the medical fluids such as acid or alkali to develop, so environment is negative
Lotus is big.Moreover, in order to form the resist layer part removed by development, it is necessary to use extra anticorrosive additive material.In addition, logical
Crossing the resist layer part that development removes becomes waste.Therefore, the amount of waste is more, and carrying capacity of environment is big.
In patent document 3, it is formed with the welding resist film of 2 layers of the LED containing white ink layer and priming coat.This is anti-
Although erosion agent film can be formed without development, need to prepare to be used to form respectively the composition of white ink layer and for shape
At the composition of priming coat, furthermore, it is desirable to be respectively coated the operation of both compositions.Therefore, the manufacture effect of electronic component etc.
Rate is poor, and the manufacturing cost of electronic component also increases.
Therefore, the material that inventor is small to carrying capacity of environment and manufacture efficiency is good is inquired into, and finds following technical problem:
When coating material on being coated with object Part forms cured film, adaptation drop of the cured film relative to coating object Part
Low or cured film heat resistance reduces.
A kind of adaptation the object of the present invention is to provide cured film relative to coating object Part can be mentioned
Height, and due to being white so that the light reflectivity of cured film can be improved, and the heat resistance of cured film accesses
The Photocurable composition of raising.In addition, the present invention also aims to provide a kind of using above-mentioned Photocurable composition
The manufacturing method of electronic component.
For solving the technical solution of technical problem
Wide in range aspect according to the present invention, provides a kind of Photocurable composition, is used for the table in coating object Part
It partly and at multiple positions is coated on face, the Photocurable composition includes: epoxy (methyl) acrylate, tool
There is 2000 or more weight average molecular weight and does not have carboxyl；Photocurable compound has at least one ethylenic unsaturated bond
And without 2000 or more weight average molecular weight, the photocurable compound is not the weight average molecular weight with 2000 or more
Epoxy (methyl) acrylate；White pigment；Photoepolymerizationinitiater initiater, the content of epoxy (methyl) acrylate are 5 weights
Measure % or more, 30 weight % or less.
In a certain particular aspects of Photocurable composition of the invention, the content of the white pigment be 20 weight % with
Upper and 70 weight % or less.
In a certain particular aspects of Photocurable composition of the invention, the Photocurable composition has at least one
(methyl) acryloyl group and do not have 2000 or more weight average molecular weight, the photocurable compound be not have 2000 or more
Weight average molecular weight epoxy (methyl) acrylate.
It is in the content of a certain particular aspects of Photocurable composition of the invention, epoxy (methyl) acrylate
10 weight % or more and 30 weight % or less.
In a certain particular aspects of Photocurable composition of the invention, the Photocurable composition, which contains, to be had at least
The sulfur-bearing alcohol-based compounds of one mercapto.
In a certain particular aspects of Photocurable composition of the invention, have 2000 contained in Photocurable composition
The ratio between content of the total content of the photo-curable ingredient of above weight average molecular weight and the photocurable compound for 1.25 with
Under.
In a certain particular aspects of Photocurable composition of the invention, the Photocurable composition passes through irradiation light simultaneously
Used after being cured, and be used to form resist film and without development.
Photocurable composition of the invention is in the viscosities il 1 and its viscosity under 25 DEG C and 10rpm under 25 DEG C and 1rpm
The ratio between η 2 is 1.1 or more and 2.2 or less.
In Photocurable composition of the invention, preferably heat cure is not carried out by the effect of thermal curing agents and used.
In a certain particular aspects of Photocurable composition of the invention, the Photocurable composition is free of Thermocurable
Compound, or contain 5 weight % Thermocurable compound below.
In a certain particular aspects of Photocurable composition of the invention, the Photocurable composition be not used in it is other
Photocurable composition is formed together the resist film of multilayer.
Wide in range aspect according to the present invention, provides a kind of manufacturing method of electronic component comprising: in electronic component body
Surface on partly and the Photocurable composition described in the coating of multiple positions, thus the process for forming composition layer；It is right
The composition layer irradiation light forms manufacturing method described in the process of cured film without making to form the cured film
The operation of the composition layer development.
In a certain particular aspects of the manufacturing method of electronic component of the invention, without to form the cured film and
Make the operation of the composition layer heat cure by the effect of thermal curing agents.
In a certain particular aspects of the manufacturing method of electronic component of the invention, the composition layer is resist layer, institute
Stating cured film is resist film.
The effect of invention
Photocurable composition of the invention includes: epoxy (methyl) acrylate, divides equally again with 2000 or more
Son is measured and is not had carboxyl；Photocurable compound, at least one ethylenic unsaturated bond and without 2000 or more
Weight average molecular weight, the photocurable compound are not epoxy (methyl) acrylic acid of the weight average molecular weight with 2000 or more
Ester；White pigment；Photoepolymerizationinitiater initiater, the content of epoxy (methyl) acrylate are 5 weight % or more and 30 weight %
Hereinafter, therefore, Photocurable composition of the invention partly and at multiple positions is coated on the surface of coating object Part
And when making its solidification, can be improved adaptation of the cured film relative to coating object Part, and due to be it is white, so as to
The light reflectivity of cured film is improved, and the heat resistance of cured film can be improved.
Detailed description of the invention
Fig. 1 (a)~(c) is for illustrating that the Photocurable composition using one embodiment of the present invention manufactures the ministry of electronics industry
The sectional view of one example of the method for part；
Fig. 2 (a)~(e) is for illustrating the method using existing developable anti-corrosion agent composition manufacture electronic component
The sectional view of one example.
Description of symbols
1 ... electronic component
2 ... resist films (cured film)
11 ... coatings object Part (electronic component body)
11A ... substrate
11B ... electrode
12 ... resist layers (composition layer)
Specific embodiment
Hereinafter, illustrating details of the invention.
[Photocurable composition]
Partly and at multiple positions coating makes photocurable compound of the invention on the surface of coating object Part
With.Photocurable composition of the invention is preferably used by irradiating photocuring, and be used to form resist film and without
Development.Photocurable composition of the invention is preferably non-developable resist Photocurable composition.Photocuring of the invention
Property composition without being developed to form resist film, with carry out for formed resist film and shown
The developable anti-corrosion agent composition of shadow is different.In Photocurable composition of the invention, using even if without development can
Obtain the composition of good resist film.
Photocurable composition of the invention includes: (A) epoxy (methyl) acrylate, and the weight with 2000 or more is equal
Molecular weight and do not have carboxyl；(B) photocurable compound, have at least one ethylenic unsaturated bond and do not have 2000 with
On weight average molecular weight, the photocurable compound be not with 2000 or more weight average molecular weight epoxy (methyl) propylene
Acid esters；(C) white pigment；(D) Photoepolymerizationinitiater initiater.
In the present invention, due to using above-mentioned composition, so can be improved cured film (resist film etc.) relative to coating
The adaptation of object Part.In the present invention, even if without development, adaptation of the cured film relative to coating object Part
It is high.For example, the adaptation of the electronic component bodies such as substrate and cured film (resist film etc.) can be improved, can inhibit to solidify
The removing of object film (resist film etc.).Moreover, Photocurable composition of the invention due to contain (C) white pigment, can
To form the cured film (resist film etc.) of white.Since cured film (resist film etc.) is white, so as to improve
The light reflectivity of cured film (resist film etc.).Moreover, using above-mentioned composition, therefore, can be improved solidification in the present invention
The heat resistance of object film (resist film etc.).For example, being able to suppress the discoloration of cured film (resist film etc.).
Moreover, the content of (A) epoxy (methyl) acrylate is 5 in 100 weight % of Photocurable composition of the invention
Weight % or more and 30 weight % or less.Therefore, adaptation of the cured film relative to coating object Part can be effectively improved.
Moreover, if the content of (A) epoxy (methyl) acrylate within the above range, is printing photocurable compositions of the invention
When object, appearance is good.In the present invention, the content of (A) epoxy (methyl) acrylate is within the above range to for high water
Flat acquisition effect of the invention is important composition.
Moreover, in the present invention, even if without exposure process and many processes such as developing procedure in photoetching, it also being capable of shape
At good cured film (resist film etc.).In the case where not being exposed process and developing procedure, it is possible to reduce discarded
The amount of object can reduce carrying capacity of environment.Furthermore, it is possible to reduce the manufacturing cost of electronic component etc..
The viscosities il 2 under viscosities il 1 and 25 DEG C and 10rpm for above-mentioned Photocurable composition, under 25 DEG C and 1rpm
The ratio between (1/ η 2 of η) be preferably 0.5 or more, more preferably 1.1 or more, further preferably 1.4 or more, and preferably 2.2 hereinafter,
More preferably 2.0 or less.Above-mentioned Photocurable composition is suitable for forming resist film and without development, therefore, above-mentioned light
Sometimes partly and at multiple positions coating makes solidification compound on the surface of the coating object Part such as electronic component body
With.For example, above-mentioned Photocurable composition is coated into pattern-like sometimes.If above-mentioned ratio (1/ η 2 of η) is above-mentioned lower limit or more
And resist film hereinafter, then can be more precisely formed in specified region by the above-mentioned upper limit.For example, even if with such as width
150 μm or less are coated into pattern-like, also can accurately form cured film (resist film etc.).Above-mentioned photocurable compositions
Object is suitable for printing to form cured film using pattern.
Above-mentioned viscosity can be used E type viscosimeter and be measured.
Using above-mentioned Photocurable composition, the light of illumination wavelength 365nm, and make accumulated light 2000mJ/cm2, from
And solidfied material is obtained, the solidfied material of acquisition is placed 5 minutes at 270 DEG C.Place the color difference Δ E of the L*a*b* color specification system of front and back
Preferably 5.0 hereinafter, more preferably 4.0 hereinafter, further preferably 3.5 hereinafter, particularly preferably 3.0 or less.If above-mentioned
Δ E is the above-mentioned upper limit hereinafter, then the heat resistance of cured film is very excellent, can be to the light of cured film caused by being used for a long time
The reduction of reflectivity is inhibited.As the lamp of the light for illumination wavelength 365nm, can enumerate metal-halide lamp, mercury vapor lamp and
LED light etc..
Above-mentioned Photocurable composition is preferably used to form the resist film of single layer.In the present invention, even if for the anti-of single layer
Agent film is lost, the resist film of discovery said effect is also capable of forming.Above-mentioned Photocurable composition is preferred for solid with other light
The property changed composition is formed together the resist film of multilayer.The resist film of the single layer formed using above-mentioned Photocurable composition is excellent
Choosing does not carry out lamination with other resist films.The resist film of multilayer is being formed using Photocurable composition of more than two kinds
In the case of, the manufacture efficiency of resist film reduces.
Above-mentioned Photocurable composition due to being solidified by the irradiation of light, can be free of Thermocurable compound,
Thermal curing agents can also be free of.Above-mentioned Photocurable composition, which does not preferably carry out heat cure by the effect of thermal curing agents, to be made
With.It can be without making to be configured at the combination being coated on object Part surface to form above-mentioned cured film (resist film etc.)
Nitride layer (resist layer etc.) carries out heat cure.Due to forming above-mentioned cured film, object portion can not be coated with to being configured at
Composition layer on the surface of part is heated.But said combination nitride layer can carry out the heating under low temperature.It is above-mentioned to be formed
Said combination nitride layer is not preferably heated to 280 DEG C or more by cured film, is not heated to 180 DEG C or more more preferably, more preferably not
It is heated to 60 DEG C or more.The temperature for heating said combination nitride layer is lower, is more able to suppress the coating such as electronic component body object portion
The heat deterioration of part.
Above-mentioned Photocurable composition contains the photo-curable ingredient of the weight average molecular weight with 2000 or more.Above-mentioned light is solid
The property changed composition at least contains (A) epoxy (methyl) acrylate as above-mentioned photo-curable ingredient, with 2000 or more
Weight average molecular weight and do not have carboxyl.Above-mentioned Photocurable composition can be containing other than (A) epoxy (methyl) acrylate
With 2000 or more weight average molecular weight photo-curable ingredient as above-mentioned photo-curable ingredient.
From the viewpoint of the adaptation for further improving cured film, in above-mentioned Photocurable composition, with weight
Benchmark meter, the total content and (B) photocurable compound of above-mentioned photo-curable ingredient contained in above-mentioned Photocurable composition
The ratio between content preferably 0.1 or more, more preferably 0.2 or more, further preferably 0.3 or more, (B) photo-curable
Closing object has at least one ethylenic unsaturated bond.In addition, from the viewpoint of the adaptation for further improving cured film,
In above-mentioned Photocurable composition, with weight basis, above-mentioned photo-curable ingredient contained in above-mentioned Photocurable composition
The ratio between total content and the content of (B) photocurable compound preferably 1.5 hereinafter, more preferably 1.25 hereinafter, further excellent
0.95 is selected as hereinafter, particularly preferably 0.7 hereinafter, (B) photocurable compound has at least one ethylene unsaturated
Key.
For the total content of the above-mentioned photo-curable ingredient contained in the above-mentioned Photocurable composition, in above-mentioned photocuring
Property composition as the photo-curable ingredient of weight average molecular weight with 2000 or more only contain (A) epoxy (methyl) acrylate
When, indicate the content of (A) epoxy (methyl) acrylate；It is equal as the weight with 2000 or more in above-mentioned Photocurable composition
The photo-curable ingredient of molecular weight contains the tool other than (A) epoxy (methyl) acrylate and (A) epoxy (methyl) acrylate
When having the photo-curable ingredient of 2000 or more weight average molecular weight, (A) epoxy (methyl) acrylate and (A) epoxy (first are indicated
Base) other than acrylate with 2000 or more weight average molecular weight photo-curable ingredient total content.
Hereinafter, illustrating each ingredient contained in above-mentioned Photocurable composition.
((A) epoxy (methyl) acrylate)
(A) epoxy (methyl) acrylate contained in above-mentioned Photocurable composition does not have carboxyl.Above-mentioned photocuring
Property composition contained in (A) epoxy (methyl) acrylate weight average molecular weight be 2000 or more.By using (A) epoxy
(methyl) acrylate, cured film are more effectively improved relative to the adaptation of coating object Part.Especially in (C) white
When pigment content is more, if not using (A) epoxy (methyl) acrylate, what the adaptation presence of cured film was easily reduced
Tendency.Cured film also can be improved even if the content of (C) white pigment is more by using (A) epoxy (methyl) acrylate
Adaptation.(A) epoxy (methyl) acrylate can be used singly or in combination of two or more.
From the viewpoint of the hardness for improving cured film, (A) epoxy (methyl) acrylate preferably comprises the ring of 2 functions
Epoxy (methyl) acrylate more than oxygen (methyl) acrylate and 3 functions.Epoxy (methyl) acrylate of 2 functions is preferred
With 2 (methyl) acryloyl groups.Epoxy (methyl) acrylate more than 3 functions preferably has 3 (methyl) acryloyl groups.
(A) epoxy (methyl) acrylate is obtained by reacting (methyl) acrylic acid and epoxide.(A) epoxy
(methyl) acrylate is obtained and epoxy group to be transformed to (methyl) acryloyl group.Above-mentioned Photocurable composition passes through photograph
It penetrates light and solidifies, therefore, (A) epoxy (methyl) acrylate does not preferably have epoxy group.
As (A) epoxy (methyl) acrylate, biphenol type epoxy (methyl) acrylate (such as bisphenol A-type can be enumerated
Epoxy (methyl) acrylate, bisphenol F type epoxy (methyl) acrylate, bisphenol S type epoxy (methyl) acrylate), cresols
Nobolak type epoxy (methyl) acrylate, amine modified bisphenol type ring oxygen (methyl) acrylate, caprolactone modification bisphenol type
Epoxy (methyl) acrylate, carboxylic acid anhydride modified epoxy (methyl) acrylate and nobolak type epoxy (methyl) acrylic acid
The such as ester
The commercially available product of epoxy (methyl) acrylate as 2 functions, can enumerate KAYARADR-381 (Japanese chemical drug strain formula
Commercial firm's manufacture, bisphenol-a epoxy acrylate), PE2100P (MIWON Co., Ltd. manufacture, bisphenol-a epoxy acrylate),
Ripoxy PC-3F (Showa Denko K. K's manufacture, bisphenol-a epoxy acrylate) and EBECRYL3708 (Daicel-
The manufacture of allnex Co., Ltd., modified bisphenol A type epoxy acrylate) etc..In addition, as epoxies (methyl) more than 3 functions
The commercially available product of acrylate can enumerate EBECRYL3603 (manufacture of Daicel-allnex Co., Ltd., epoxy novolac acrylic acid
Ester) etc..Alternatively, it is also possible to pass through the hydroxyl modification of the epoxy for making 2 functions (methyl) acrylate and importing (methyl) acryloyl
Base obtains epoxy (methyl) acrylate of 3 functions or more.
" (methyl) acryloyl group " indicates acryloyl group and methylacryloyl." (methyl) acrylic acid " indicate acrylic acid and
Methacrylic acid." (methyl) acrylate " indicates acrylate and methacrylate.
(A) weight average molecular weight of epoxy (methyl) acrylate is 2000 or more.(A) weight of epoxy (methyl) acrylate
When average molecular weight is lower than 2000, there are the tendencies that the adaptation of cured film is deteriorated.(A) weight of epoxy (methyl) acrylate is equal
Molecular weight is preferably 20000 or less.It is however possible to use (A) epoxy (methyl) acrylic acid that weight average molecular weight is 2000 or more
Ester, and epoxy (methyl) acrylate using weight average molecular weight lower than 2000.(A) weight of epoxy (methyl) acrylate is equal
Molecular weight is preferably 3000 or more, and more preferably 5000 or more.
Weight average molecular weight is the weight average molecular weight measured in terms of polystyrene by gel permeation chromatography (GPC), can be passed through
Following measurement device and determination condition measures.
Measurement device: " the Waters GPC System (Waters2690+ of Japanese Waters Co., Ltd. manufacture
Waters2414(RI))”
Determination condition column: GPCLF-G × 1 piece Shodex, GPCLF-804 × 2 piece Shodex
Mobile phase: THF 1.0mL/ minutes
Sample concentration: 5mg/mL
Detector: differential refraction rate detector (RID)
Standard substance: polystyrene (manufacture of TOSOH Co., Ltd., molecular weight: 620~590000)
(A) epoxy (methyl) acrylate can be the hydroxyl of epoxy (methyl) acrylate with hydroxyl by being modified
Made of epoxy (methyl) acrylate.In this case, the degree of cross linking can be improved, and hardness can be improved.As can be used for changing
The compound of property, can enumerate silane coupling agent and the monomer with isocyanate group etc..As above-mentioned silane coupling agent, can enumerate
With vinyl, (methyl) acryloyl group, styryl, sulfydryl, epoxy group, amino, thioether group, urea groups and isocyanate group
The compound etc. of equal functional groups.Due to there is photoreactivity, it is advantageous to vinyl, (methyl) acryloyl group, styryl,
Or the compound of sulfydryl.As the monomer with isocyanate group, can enumerate with vinyl, (methyl) acryloyl group, benzene second
Alkenyl or the compound of sulfydryl etc..
(A) epoxy (methyl) acrylate does not have carboxyl.By using epoxy (methyl) acrylic acid for not having carboxyl
Ester can prevent the carboxyl bring baneful influence in cured film, such as be able to suppress the discoloration of cured film.
In above-mentioned 100 weight % of Photocurable composition, the content of (A) epoxy (methyl) acrylate be 5 weight % with
Upper and 30 weight % or less.In above-mentioned 100 weight % of Photocurable composition, the content of (A) epoxy (methyl) acrylate is excellent
It is selected as 10 weight % or more.(A) when the content of epoxy (methyl) acrylate is above-mentioned lower limit or more, the adaptation of solidfied material has
It improves on effect ground.(A) when the content of epoxy (methyl) acrylate is the above-mentioned upper limit or less, the pencil hardness of cured film is effectively
It improves, is easier to obtain uniform film in printing.In addition, from the viewpoint of the adaptation for effectively improving cured film,
In above-mentioned 100 weight % of Photocurable composition, epoxy (methyl) acrylate for 2 functions that weight average molecular weight is 2000 or more
The total content of epoxy (methyl) acrylate more than 3 functions for being 2000 or more with weight average molecular weight is preferably 5 weight %
More than, more preferably 10 weight % or more, and preferably 30 weight % or less.
(photocurable compound that (B) has at least one ethylenic unsaturated bond)
By the way that (B) to be had to the photocurable compound and (A) epoxy (methyl) propylene of at least one ethylenic unsaturated bond
Acid esters is used together, even if the content of (C) white pigment is more, can also effectively improve the adaptation of cured film, moreover, holding
Easily the viscosity ratio of Photocurable composition (1/ η 2 of η) is controlled in optimum range.(B) have at least one olefinic unsaturated
Epoxy (methyl) acrylate without the weight average molecular weight with 2000 or more in the photocurable compound of key.(B) have
The photocurable compound of at least one ethylenic unsaturated bond can be used alone, and can also combine two or more.
(B) photocurable compound at least one ethylenic unsaturated bond does not have 2000 or more Weight-average molecular
Amount.Therefore, the molecular weight that (B) there is the photocurable compound of at least one ethylenic unsaturated bond to preferably have less than 2000.
(B) molecular weight of photocurable compound is preferably 1000 hereinafter, more preferably 800 hereinafter, further preferably 600 or less.
It should be noted that molecular weight refers in the present invention: being the value calculated in the case where that can be calculated according to molecular structure, not
It is weight average molecular weight in the case where capable of being calculated according to molecular structure.
From the viewpoint of the adaptation for further improving cured film, (B) has at least one ethylenic unsaturated bond
Photocurable compound be preferably that there is the photocurable compound of at least one (methyl) acryloyl group.(B) have at least
Preferably there is the photocurable compound of one ethylenic unsaturated bond at least one (methyl) acryloyl group to be used as containing olefinic not
The group of saturated bond.
There is the photocurable compound of at least one ethylenic unsaturated bond as (B), be not particularly limited, can enumerate:
(methyl) acrylic acid adduct, polyurethane of (methyl) acrylic acid adduct of polyalcohol, the epoxyalkane modifier of polyalcohol
(methyl) acrylate and polyester (methyl) acrylate etc..It as above-mentioned polyalcohol, can enumerate: diethylene glycol, three second two
Alcohol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, trimethylolpropane, cyclohexanedimethanol, tristane diformazan
Alcohol, the alkylene oxide adducts of bisphenol-A and pentaerythrite etc..(B) in photocurable compound, a part of hydroxyl can be remained.
From the viewpoint of the adaptation for further improving cured film, Photocurable composition can contain polyurethane
(methyl) acrylate or polyester (methyl) acrylate.
From the viewpoint of the adaptation for further improving cured film, preferably (B) has at least one olefinic insatiable hunger
Contain the photocurable compound that (B1) has an ethylenic unsaturated bond with the photocurable compound of key.
(B) photocurable compound at least one ethylenic unsaturated bond can be containing (B2) with 2 or more
The photocurable compound of ethylenic unsaturated bond can also have the photocuring of 3 or more ethylenic unsaturated bonds containing (B3)
Property compound.From the viewpoint of the adaptation for further improving cured film, (B) has at least one ethylenic unsaturated bond
Photocurable compound preferably comprise the photocurable compound of (B1) with an ethylenic unsaturated bond and (B2) there are 2
The photocurable compound of above ethylenic unsaturated bond.
From the viewpoint of the adaptation for further improving cured film, (B) has at least one ethylenic unsaturated bond
Photocurable compound preferably comprise ester ring type compound, alternatively, contain aromatic rings or hydroxyl.Although it is preferred that simple function at
Point, but the polyfunctional Multiple components such as two functions can be contained.
(B) photocurable compound at least one sub- A Hu unsaturated bond does not preferably have carboxyl.By using
Photocurable compound without carboxyl can prevent the carboxyl bring baneful influence in cured film, be able to suppress example
Such as the discoloration of cured film.
(B) viscosity of the photocurable compound at least one ethylenic unsaturated bond at 25 DEG C is preferably 1mPa
S or more, more preferably 3mPas or more.From the viewpoint of the adaptation further by cured film, (B) has extremely
Viscosity of the photocurable compound of a few ethylenic unsaturated bond at 25 DEG C is preferably 200mPas hereinafter, more preferably
100mPas or less.
Above-mentioned viscosity can be used E type viscosimeter and measure under conditions of 25 DEG C and 10rpm.
In above-mentioned 100 weight % of Photocurable composition, (B) has the photo-curable of at least one ethylenic unsaturated bond
The content for closing object is preferably 5 weight % or more, more preferably 10 weight % or more, and preferably 50 weight % are hereinafter, more preferably
For 40 weight % or less.Under (if B) there is the content of the photocurable compound of at least one ethylenic unsaturated bond to be above-mentioned
More than limit and the above-mentioned upper limit is hereinafter, then the physical property of cured film effectively improves.
In above-mentioned 100 weight % of Photocurable composition, (B1) has the photo-curable chemical combination of an ethylenic unsaturated bond
The content of object is preferably 10 weight % or more, more preferably 20 weight % or more, and preferably 50 weight % are hereinafter, more preferably
40 weight % or less.If it is above-mentioned lower limit that (B1), which has the content of the photocurable compound of at least one ethylenic unsaturated bond,
Above and the above-mentioned upper limit is hereinafter, then the adaptation of cured film effectively improves.
In above-mentioned 100 weight % of Photocurable composition, (B3) has the light of the ethylenic unsaturated bond of at least three or more solid
The content of the property changed compound is preferably 5 weight % or more, and preferably 20 weight % or less.If (B3) is with 3 or more
The content of the photocurable compound of ethylenic unsaturated bond be above-mentioned lower limit or more and the above-mentioned upper limit hereinafter, then cured film it is close
Conjunction property effectively improves.
((C) white pigment)
Since above-mentioned Photocurable composition contains (C) white pigment, so as to form the high solidfied material of light reflectivity
Film.By using (C) white pigment, with the filler being used only other than (C) white pigment the case where compared with, light can be obtained
The high cured film of reflectivity.(C) white pigment can be used alone, and can also combine two or more.
As (C) white pigment, aluminium oxide, titanium oxide, zinc oxide, zirconium oxide, antimony oxide and magnesia etc. can be enumerated.
From the viewpoint of the light reflectivity for further improving cured film, (C) white pigment is preferably titanium oxide, oxygen
Change zinc, barium sulfate, calcium carbonate, talcum or zirconium oxide.Using the preferred white pigment, titanium oxide, zinc oxide,
In barium sulfate, calcium carbonate, talcum and zirconium oxide, one kind or two or more white pigment can be used.(C) white pigment is preferably
Titanium oxide or zinc oxide, preferably titanium oxide, and preferably zinc oxide.(C) white pigment can be zirconium oxide.
Above-mentioned titanium oxide is preferably Titanium Dioxide Rutile Top grade.By using Titanium Dioxide Rutile Top grade, cured film it is heat-resisting
Property further improves, and can further inhibit the discoloration of cured film.
Above-mentioned titanium oxide is preferably the gold being surface-treated using aluminium tungsten oxide, zirconium tungsten oxide or Si oxide etc.
Red stone-type titanium oxide.By using above-mentioned surface treated Titanium Dioxide Rutile Top grade, the heat resistance of cured film is further
It improves.
It as above-mentioned surface treated Titanium Dioxide Rutile Top grade, such as can enumerate: as rutile chlorine method titanium oxide
Ishihara Sangyo Kaisha, Ltd. manufacture " CR-90-2 ", as rutile chlorine method titanium oxide Ishihara Sangyo Kaisha, Ltd. manufacture
" CR-58 ", as rutile sulfuric acid process titanium oxide Dupont Co., Ltd. manufacture " R-900 " and as rutile sulphur
" R-630 " etc. of Ishihara Sangyo Kaisha, Ltd.'s manufacture of acid oxidation titanium.White pigment other than Titanium Dioxide Rutile Top grade can be with
It is carried out similarly surface treatment.
From the viewpoint of the adaptation and intensity for further improving cured film, (C) white pigment can contain aerobic
Change titanium and the white pigment different from titanium oxide.
The method of above-mentioned surface treatment is not particularly limited.As the method for surface treatment, dry method, wet type can be used
Method, integral blend method and other well-known usual surface treatment methods.
(C) average grain diameter of white pigment is preferably 0.1 μm or more, and preferably 40 μm or less.If above-mentioned average grain
Diameter is above-mentioned lower limit or more and the above-mentioned upper limit hereinafter, then can further improve the light reflectivity of cured film.
In above-mentioned 100 weight % of Photocurable composition, the content of (C) white pigment is preferably 20 weight % or more, more
Preferably 30 weight % or more, further preferably 40 weight % or more, and preferably 70 weight % are hereinafter, more preferably 60 weights
Measure % or less.If the content of (C) white pigment be above-mentioned lower limit more than and the above-mentioned upper limit hereinafter, if cured film light reflection
Rate further improves, and the adaptation of above-mentioned cured film further improves.Above-mentioned 100 weight % of Photocurable composition
In, the content of (C) white pigment can be 50 weight % or more.
In the present invention, using specific composition, therefore, even if the content of (C) white pigment increases, solidification also can be improved
The adaptation of object film.For example, in above-mentioned 100 weight % of Photocurable composition, even if the content of (C) white pigment is 50 weights
% or more is measured, the adaptation of cured film also can be sufficiently improved.
From the further adaptation for improving cured film, and further improve the viewpoint of the light reflectivity of cured film
It sets out, in above-mentioned Photocurable composition, with weight basis, the content and (A) epoxy (methyl) acrylic acid of (C) white pigment
The ratio between content of ester is preferably 0.5 or more, more preferably 1.0 or more, further preferably 1.5 or more.It is improved from further
From the perspective of the adaptation of cured film, in above-mentioned Photocurable composition, with weight basis, (C) white pigment contains
The ratio between amount and the content of (A) epoxy (methyl) acrylate preferably 10 is hereinafter, more preferably 5.0 hereinafter, further preferably
4.0 following.
In the case where above-mentioned (C) white pigment contains titanium oxide, from the further adaptation for improving cured film, and
From the perspective of the light reflectivity for further improving cured film, in above-mentioned Photocurable composition, with weight basis, oxygen
Change the ratio between the content of the content of titanium relative to (C) white pigment preferably 0.4 or more, more preferably 0.6 or more, further preferably
It is 0.8 or more.From the viewpoint of the adaptation for further improving cured film, in above-mentioned Photocurable composition, with weight
Benchmark meter is measured, the ratio between the content of titanium oxide and the content of (C) white pigment are preferably 1.0 or less.
((D) Photoepolymerizationinitiater initiater)
Above-mentioned Photocurable composition contains (D) Photoepolymerizationinitiater initiater, therefore, photo-curable group can be made by irradiation light
Close object solidification.(D) Photoepolymerizationinitiater initiater can be used alone, and can also combine two or more.
As (D) Photoepolymerizationinitiater initiater, can enumerate: acylphosphine oxide, halogenated methylation triazine, halomethylation dislike two
Azoles, imidazoles, benzoin, benzoin alkylether, anthraquinone, benzanthrone, benzophenone, alkyl phenones, thioxanthones, benzoic ether,
Acridine, azophenlyene, luxuriant titanium, alpha-aminoalkyl benzophenone, oxime and their derivative.
As benzophenone Photoepolymerizationinitiater initiater, o-benzoyl yl benzoic acid methyl esters and meter Xi Leshi ketone Chi can be enumerated
Deng.As the commercially available product of benzophenone Photoepolymerizationinitiater initiater, EAB (Baotugu Chemical Industrial Co., Ltd's manufacture) can be enumerated
Deng.
As the commercially available product of alkyl phenones system Photoepolymerizationinitiater initiater, can enumerate: Darocur1173, Darocur2959,
Irgacure184, Irgacure907, Irgacure369, Irgacure651 (manufacture of BASF Co., Ltd.) and
Esacure1001M (manufacture of Lamberti Co., Ltd.) etc..
As the commercially available product of acylphosphine oxide Photoepolymerizationinitiater initiater, Lucirin TPO (BASF Co. Ltd. system can be enumerated
Make) and Irgacure819 (manufacture of BASF Co., Ltd.) etc..
As the commercially available product of thioxanthene ketone class Photoepolymerizationinitiater initiater, isopropyl thioxanthone and diethyl thioxanthone etc. can be enumerated.
As the commercially available product of oxime esters Photoepolymerizationinitiater initiater, IrgacureOXE-01 and IrgacureOXE-02 can be enumerated
(manufacture of BASF Co., Ltd.) etc..
From the viewpoint of the adaptation for further improving cured film, (D) Photoepolymerizationinitiater initiater preferably comprises acyl group
Phosphine Photoepolymerizationinitiater initiater and alkylbenzene ketone Photoepolymerizationinitiater initiater both.
Inhibit to foam, removing and discoloration from the viewpoint of further, (D) Photoepolymerizationinitiater initiater preferably comprises alkylbenzene
Ketone Photoepolymerizationinitiater initiater and acylphosphine oxide class Photoepolymerizationinitiater initiater both, further preferably contain acylphosphine oxide class light
Polymerization initiator and double oxide-based Photoepolymerizationinitiater initiater of acylphosphine oxide both.
There is the photo-curable of at least one ethylenic unsaturated bond relative to (A) epoxy (methyl) acrylate and (B)
It closes object and amounts to 100 parts by weight, the content of (D) Photoepolymerizationinitiater initiater is preferably 1 parts by weight or more, and it is more than more preferably 3 parts by weight,
And preferably 20 parts by weight are hereinafter, below more preferably 15 parts by weight.If the content of (D) Photoepolymerizationinitiater initiater is above-mentioned lower limit
Above and the above-mentioned upper limit is hereinafter, then can make Photocurable composition carry out photocuring well.
From the viewpoint of the curability of inside and both outer surfaces for further increasing solidfied material, (D) photopolymerization is drawn
Hair agent preferably combine be employee two or more.Photocurable composition preferably comprises Photoepolymerizationinitiater initiater of more than two kinds.It is specific and
Speech, more preferable Irgacure819 (bis- (2,4,6- trimethylbenzoyl)-phenylphosphine oxides, the manufacture of BASF Co., Ltd.),
TPO (2,4,6- trimethylbenzoy-dipheny-phosphine oxide, the manufacture of BASF Co., Ltd.), Esacure1001M (1- [4-
(4- benzoyl) phenyl] -2- methyl -2- (4- methylphenylsulfonyl) propane -1- ketone, the manufacture of Lamberti Co., Ltd.),
The group of Darocur1173, Darocur2959, Irgacure907, Irgacure369, Irgacure651 or Irgacure184
It closes.In this case, the content of Irgacure819 is in the 100 weight % of (D) Photoepolymerizationinitiater initiater total amount, preferably 1 weight %
More than, more preferably 15 weight % or more, and preferably 99 weight % are hereinafter, more preferably 85 weight % or less.Furthermore it is possible to
Use Irgacure819 as essential component, and 3 kinds or more of Photoepolymerizationinitiater initiater is applied in combination.In this case,
The lower limit and the upper limit of the preferred content of Irgacure819 are identical as above-mentioned value.
(the sulfur-bearing alcohol-based compounds that (E) has at least one mercapto)
By to (E) there are the sulfur-bearing alcohol-based compounds of at least one mercapto and other compounds to be combined use,
The excellent cured film of moisture-proof can be obtained, and the high cured film of heat resistance can be obtained.Moreover, by (E) sulfur-bearing
Alcohol-based compounds with use is combined by the Titanium Dioxide Rutile Top grade that chlorine method manufactures, the adaptation of cured film can be had both
With the storage stability of Photocurable composition.(E) sulfur-bearing alcohol-based compounds can be used alone, and can also be applied in combination 2
Kind or more.
It as the concrete example of (E) sulfur-bearing alcohol-based compounds, can enumerate: the trihydroxy methyl of SC organic chemistry Co., Ltd. manufacture
Propane three (3-thiopropionate) (TMMP), pentaerythrite four (3-thiopropionate) (PEMP), three [(3- mercaptopropionyl oxygen
Base)-ethyl] isocyanuric acid ester (TEMPIC), tetraethylene glycol bis- (3-thiopropionates) (EGMP-4), six (3- of dipentaerythritol
Mercaptopropionic acid ester) the primary multi-functional thiol such as (DPMP), Showa Denko K. K's manufacture (the 3- mercaptobutyric acid of pentaerythrite four
Ester) (Karenz MTPE1), 1,3,5- tri- (3- sulfydryl bytyry oxygroup ethyl) -1,3,5-triazines -2,4,6 (1H, 3H, 5H) -
The secondary multi-functional thiols such as bis- (the 3- sulfydryl bytyry oxygroup) butane (Karenz MTBD1) of triketone (Karenz MTNR1), 1,4-,
(β-mercaptopropionic acid (BMPA), 3- mercapto-propionate (MPM), the 3- mercaptopropionic acid 2- second of SC organic chemistry Co., Ltd. manufacture
The own ester of base (EHMP), 3- mercaptopropionic acid n-octyl (NOMP), methoxybutyl -3-thiopropionate (MBMP), 3- mercaptopropionic acid
Simple functions mercaptan such as stearyl (STMP) etc..
From the further moisture-proof for improving cured film, from the perspective of the adaptation for improving cured film, (E) has
The sulfur-bearing alcohol-based compounds of at least one mercapto preferably comprise the mercaptan compound of (E1) with 2 or more mercaptos.
In above-mentioned 100 weight % of Photocurable composition, the content of (E) sulfur-bearing alcohol-based compounds and (E1) mercaptan compound
It is respectively preferably 0.1 weight % or more, more preferably 0.5 weight % or more, and preferably 10 weight % are hereinafter, more preferably 5
Weight % or less.Relative to 100 parts by weight of (A) epoxy (methyl) acrylate, (E) sulfur-bearing alcohol-based compounds and (E1) are Thiolation
The content for closing object is respectively preferably 1.0 parts by weight or more, it is more than more preferably 3.0 parts by weight, and preferably 35 parts by weight hereinafter,
More preferably 25 parts by weight are hereinafter, below further preferably 20 parts by weight.Relative to (A) epoxy (methyl) acrylate and
(B) the content difference of 100 parts by weight that photoreactive compound amounts to, (E) sulfur-bearing alcohol-based compounds and (E1) mercaptan compound
More than preferably 0.2 parts by weight, more than more preferably 1 parts by weight, and preferably 20 parts by weight are hereinafter, more preferably 10 parts by weight
Hereinafter, below further preferably 6 parts by weight.If the content of (E) sulfur-bearing alcohol-based compounds and (E1) mercaptan compound is upper
State lower limit or more and the above-mentioned upper limit hereinafter, then cured film moisture-proof improve, can further inhibit the removing of cured film,
Furthermore, it is possible to have both the adaptation of cured film and the storage stability of Photocurable composition with high level.In addition, if
(E) content of sulfur-bearing alcohol-based compounds and (E1) mercaptan compound is the above-mentioned upper limit hereinafter, being then not easy to carry out gel in preservation
Change.If the content of (E) sulfur-bearing alcohol-based compounds and (E1) mercaptan compound is above-mentioned lower limit or more, curability is further
It improves., it is preferable to use secondary mercaptan compound from the viewpoint of improving storage stability.Go out from the viewpoint for improving storage stability
Hair, can be used polymerization inhibitor.
((F) Thermocurable compound)
Above-mentioned Photocurable composition is preferably free of (F) Thermocurable compound, or contains 5 weight % (F) below
Thermocurable compound.In the present invention, in use (F) Thermocurable compound, (F) Thermocurable compound is preferably reduced
Usage amount.Just the content of (F) Thermocurable compound is containing for 5 weight % composition below and (F) Thermocurable compound
For the amount for example, composition of 10 weight % or more, the basic physical properties of solidfied material are usually different.(F) Thermocurable chemical combination
Object can be used singly or in combination of two or more.
As (F) Thermocurable compound, epoxide etc. can be enumerated.
Above-mentioned Photocurable composition is preferably free of epoxide, or contains 5 weight % epoxides below.
Inhibit to foam, removing and discoloration from the viewpoint of further, in 100 weight % of Photocurable composition, (F)
The fewer the content of Thermocurable compound the better.In 100 weight % of Photocurable composition, (F) Thermocurable compound contains
Preferably 3 weight % are measured hereinafter, more preferably 1 weight % is hereinafter, further preferably 0.5 weight % is hereinafter, particularly preferably 0
Weight % (unused).In 100 weight % of Photocurable composition, the content of epoxide is preferably 3 weight % hereinafter, more
Preferably 1 weight % hereinafter, further preferably 0.5 weight % hereinafter, particularly preferably 0 weight % (unused).
((G) organic solvent)
Above-mentioned Photocurable composition can contain (G) organic solvent, can also be free of (G) organic solvent.
Above-mentioned Photocurable composition can be free of (G) organic solvent, or organic molten containing 10 weight % (G) below
Agent.
From the viewpoint of the adaptation for further improving cured film, in 100 weight % of Photocurable composition,
(G) the fewer the content of organic solvent the better.In 100 weight % of Photocurable composition, the content of (G) organic solvent is preferably 3
Weight % hereinafter, more preferably 1 weight % hereinafter, further preferably 0.5 weight % hereinafter, particularly preferably 0 weight % (not
Using).
(other ingredients)
Above-mentioned Photocurable composition can contain organic solvent, can also be free of organic solvent.
Above-mentioned Photocurable composition in addition to above-mentioned ingredient, can also containing other than white pigment inorganic filler,
Organic filler, colorant, polymerization inhibitor, chain-transferring agent agent, auxiliary curing agent, antioxidant, ultraviolet absorbing agent, defoaming agent,
Levelling agent, slipping agent, anti-blocking agent, paraffin, screening agent, deodorant, aromatic, preservative, antibacterial agent, resists surfactant
Electrostatic agent and adaptation imparting agent etc..As above-mentioned adaptation imparting agent, silane coupling agent etc. can be enumerated.
From the viewpoint of the adaptation and intensity for further improving cured film, photocurable compound can also contain
Inorganic filler that is different from titanium oxide and not being white pigment.
[manufacturing method of electronic component and electronic component]
The manufacturing method of electronic component include: above-mentioned Photocurable composition is coated on the surface of electronic component body and
The process for forming composition layer；The process that cured film is formed to said combination nitride layer irradiation light.The manufacturer of electronic component
In method, preferably without making said combination nitride layer develop to form above-mentioned cured film.It is preferred that said combination nitride layer is against corrosion
Oxidant layer, and preferably above-mentioned cured film is resist film.
Above-mentioned Photocurable composition is suitable for forming cured film without development, therefore, can be in electronic component
Partly and at multiple positions above-mentioned Photocurable composition is coated on the surface of main body.
From the viewpoint of the heat deterioration for preventing electronic component body, to form above-mentioned cured film, preferably do not make above-mentioned
Composition layer passes through the effect heat cure of thermal curing agents.
Hereinafter, being described with reference to the manufacturing method of specific electronic component of the invention.In embodiment party described below
In formula, said combination nitride layer is resist layer, and above-mentioned cured film is resist film.To form resist film, non-development is used
Type resist Photocurable composition.
Firstly, preparing coating object Part 11 as shown in Fig. 1 (a).Being coated with object Part 11 is electronic component body.Make
To be coated with object Part 11, using substrate 11A, multiple electrodes 11B is configured on the surface of substrate 11A.
Secondly, being coated with non-developable resist photo-curable on the surface of coating object Part 11 as shown in Fig. 1 (b)
Composition is formed resist layer 12 (composition layer).In Fig. 1 (b), partly and more on the surface of coating object Part 11
A position is coated with above-mentioned non-developable resist Photocurable composition, forms multiple resist layers 12.Specifically, in substrate
Multiple resist layers 12 are formed between multiple electrodes 11B on the surface of 11A.Resist layer 12 is, for example, resist pattern.
For example, resist layer 12 only resists with what residual after development was formed it is assumed that when using existing developable anti-corrosion agent composition
The corresponding position in erosion oxidant layer part is formed.Using existing developable anti-corrosion agent composition, not by development remove with
The corresponding position in resist layer part forms resist layer 12.
The coating method of non-developable resist Photocurable composition can for example enumerate the coating method using distributor,
The coating method of silk-screen printing and the coating method etc. for utilizing ink discharge device.From the viewpoint of manufacture efficiency is excellent, preferred silk
Wire mark brush.It is preferred that carrying out pattern printing to non-developable resist Photocurable composition.
Secondly, to 12 irradiation light of resist layer.For example, from opposite with coating 11 side of object Part of resist layer 12 one
12 irradiation light of lateral resist layer.As a result, resist layer 12 carries out photocuring as shown in Fig. 1 (c), resist film 2 is formed
(cured film).Resist film 2 is formed on the surface of coating object Part 11 (electronic component body) as a result, obtaining
Electronic component 1.
In addition, the use of the manufacturing method of Fig. 1 (a)~(c) electronic component for having resist film illustrated is an example,
The manufacturing method of electronic component can be suitable for changing.When manufacturing electronic component, be preferably formed as resist film and without development.
Using non-developable resist Photocurable composition of the invention and when manufacturing electronic component, can be coated with
2 layers or more of resist layer is formed on the surface of object Part, which can be partly and in multiple portions
Position is formed.At this point it is possible to one layer of non-developable resist Photocurable composition of every coating on the surface of coating object Part
When irradiation light, formed resist layer, alternatively, it is also possible to carried out 2 layers or more coating after irradiation light and form resist layer.
In addition, currently, using developable anti-corrosion agent composition more.In the feelings of the developable anti-corrosion agent composition using minus
Under condition, as shown in Fig. 2 (a), such as prepare coating object Part 111, with substrate 111A and the table for being configured at substrate 111A
Electrode 111B on face.Secondly, being integrally formed resist layer on the surface of coating object Part 111 as shown in Fig. 2 (b)
112.Then, as shown in Fig. 2 (c), across mask 113 only to 112 irradiation light of resist layer on electrode 111B.Then, such as Fig. 2
(d) shown in, develop, the resist layer 112 between electrode 111B is partially removed in.Partially remove resist layer
After 112, make remaining 112 heat cure of resist layer.As a result, obtaining as shown in Fig. 2 (e) in coating object Part 111
On the surface of (electronic component body), it is formed with the electronic component 101 of resist film 102.
As it appears from the above, using developable anti-corrosion agent composition, the formation efficiency of resist film and the ministry of electronics industry
The manufacture efficiency of part is poor.And develop.
In contrast, by using Photocurable composition of the invention, it can be improved cured film (resist film etc.)
Formation efficiency and electronic component manufacture efficiency.In addition it does not need to develop.
In addition, as electronic component, can also make in the present invention and have above-mentioned cured film as the anti-of optical reflection film
Penetrate plate.In electronic component, above-mentioned cured film can be used as optical reflection film, also can be only fitted to the position for reflected light.Electricity
Subassembly can also have illumination part.When using above-mentioned cured film reflected light, above-mentioned cured film can be exposed, or
It can also be with stacked laminated transparent component.
Hereinafter, enumerating Examples and Comparative Examples specifically describes the present invention.The present invention is not limited to embodiments below.
(embodiment 1~17 and comparative example 1~7)
(1) preparation of non-developable resist Photocurable composition
Cooperate gradation composition shown in table 1~3 below by use level shown in table 1~3 below, prepares non-developable
Resist Photocurable composition.
(2) preparation of electronic component
Prepare the substrate that 100mm × 100mm × thickness 0.8mm FR-4 superimposed layer has copper foil.On the substrate, silk is utilized
The version of net print process and the terylene twill system (Port リ エ ス テ Le バ イ ア ス system) using 255 meshes, with mask to non-developable
Resist Photocurable composition carries out pattern printing, forms resist layer.After printing, the purple for being provided with high-pressure mercury-vapor lamp is used
Outer beam irradiating apparatus makes accumulated light 2000mJ/cm to the ultraviolet light of resist layer illumination wavelength 365nm2, and make its
Belt conveying type exposer is by primary, thus to obtain the resist film as measurement sample.The thickness of the resist film of acquisition
It is 20 μm.
(evaluation)
(1) coating accuracy (viscosity (ratio (1/ η 2 of η)))
For the Photocurable composition of acquisition, using E type viscosimeter to Photocurable composition under 25 DEG C and 1rpm
Viscosities il 1 and 25 DEG C and 10rpm under viscosities il 2 be measured.Find out ratio (1/ η 2 of η).
(2) coating accuracy (L/S (μm))
Using be patterned with 500 μm, 300 μm, 200 μm, 150u μm, the mask of the L/S of 100 μm of each line width carry out screen printing
Brush and exposure, it is thus identified that the printing precision of L/S.Determined by following.
If resin will not be flowed between line and line, line is the state being able to confirm that, and does not flow into tree between wide and width
The line width for the state that rouge is able to confirm that interval is set as qualified, and records line width numerical value.
(3) adaptation (gridiron pattern test)
For the electronic component of acquisition, by drawing lattice tape test (JIS 5600) confirmation, and it is based on following determinating references
Confirmation.With the interval 1mm chessboard trellis solidfied material is made with 20 pieces of amount cutting cut marks, then, with cut mark part
Solidfied material is sufficiently bonded adhesive tape (JIS Z1522), and one end of adhesive tape is removed with 60 degree of angle strength, confirms stripped shape
State.Classified according to JIS to exfoliated state.In the case where classification 01,2, the quantity of the grid of removing is 0.
(4) adaptation (PCT test 96h)
After measurement sample is placed 96 hours under conditions of 121 DEG C, 2atm, whether there is or not removings for confirmation evaluation sample.
[determinating reference of PCT test 96h]
Zero: there is no the film strippings of resist
×: there are the removings of resist film
(5) uniformity of film
The Photocurable composition of acquisition is coated in support part with 20 μm of thickness.To the photo-curable group after coating
The ultraviolet light for closing object illumination wavelength 365nm, makes accumulated light 2000mJ/cm2, obtain solidfied material.Confirm the solidfied material obtained
Appearance.
[determinating reference for applying film uniformity]
Zero: meet × determinating reference other than
×: surface confirms multiple concave-convex or muscle
(6) reflectivity (Y (%))
For the electronic component of acquisition, color/colour difference meter (" CR- of KONICA MINOLTA Co., Ltd. manufacture is used
400 ") the reflectivity Y value of sample is measured and evaluated.
(7) heat resistance (reflectivity (Δ E))
The Photocurable composition of acquisition is coated in support part, 20 μm of its thickness is made.It is solid for the light after coating
The property changed composition, the ultraviolet light of illumination wavelength 365nm make accumulated light 2000mJ/cm2, to obtain solidfied material, will obtain
Solidfied material placed 5 minutes at 270 DEG C.The color difference Δ in the L*a*b* color specification system for placing front and back is acquired using color colorimeter
E。
(8) pencil hardness
The Photocurable composition of acquisition is coated in support part, 20 μm of its thickness is made.It is solid for the light after coating
The ultraviolet light of the property changed composition illumination wavelength 365nm, makes accumulated light 2000mJ/cm2, obtain solidfied material.For acquisition
Solidfied material seeks pencil hardness on the basis of JIS K5600-5-4.
Composition and result are shown in following table 1~3.
Claims (14)
1. a kind of Photocurable composition is used to partly and at multiple positions be applied on the surface in coating object Part
Cloth,
The Photocurable composition includes:
Epoxy (methyl) acrylate has 2000 or more weight average molecular weight and does not have carboxyl；
Photocurable compound, at least one ethylenic unsaturated bond and without 2000 or more weight average molecular weight, institute
Stating photocurable compound not is epoxy (methyl) acrylate of the weight average molecular weight with 2000 or more；
White pigment；
Photoepolymerizationinitiater initiater,
The content of epoxy (methyl) acrylate is 5 weight % or more and 30 weight % or less.
2. Photocurable composition as described in claim 1, wherein
The content of the white pigment is 20 weight % or more and 70 weight % or less.
3. Photocurable composition as claimed in claim 1 or 2 has at least one (methyl) acryloyl group and does not have
2000 or more weight average molecular weight, the photocurable compound are not the epoxy (first of the weight average molecular weight with 2000 or more
Base) acrylate.
4. Photocurable composition according to any one of claims 1 to 3, wherein
The content of epoxy (methyl) acrylate is 10 weight % or more and 30 weight % or less.
5. Photocurable composition as described in any one of claims 1 to 4 contains containing at least one mercapto
Mercapto compound.
6. such as Photocurable composition according to any one of claims 1 to 5, wherein
There is total content and the institute of the photo-curable ingredient of 2000 or more weight average molecular weight contained in Photocurable composition
Stating the ratio between content of photocurable compound is 1.25 or less.
7. being non-developable resist photo-curable group such as Photocurable composition according to any one of claims 1 to 6
Object is closed,
The Photocurable composition is used by irradiation light and after being cured, and be used to form resist film and without aobvious
Shadow.
8. such as Photocurable composition according to any one of claims 1 to 7, viscosities il 1 under 25 DEG C and 1rpm and its
The ratio between viscosities il 2 under 25 DEG C and 10rpm is 1.1 or more and 2.2 or less.
9. the effect for not passing through thermal curing agents carries out heat such as Photocurable composition according to any one of claims 1 to 8
Solidify and uses.
10. being free of Thermocurable compound, Huo Zhehan such as Photocurable composition according to any one of claims 1 to 9
There is 5 weight % Thermocurable compound below.
11. being not used in and other photocurable compositions such as Photocurable composition according to any one of claims 1 to 10
Object is formed together the resist film of multilayer.
12. a kind of manufacturing method of electronic component comprising:
Partly and at multiple positions light described in any one of claim 1~11 is coated on the surface of electronic component body
Solidification compound, thus the process for forming composition layer；
To the composition layer irradiation light, the process for forming cured film,
Operation of the manufacturing method without making the composition layer development to form the cured film.
13. the manufacturing method of electronic component as claimed in claim 12, wherein
Effect without passing through thermal curing agents to form the cured film makes the operation of the composition layer heat cure.
14. the manufacturing method of electronic component as described in claim 12 or 13, wherein
The composition layer is resist layer,
The cured film is resist film.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014-139202 | 2014-07-04 | ||
| JP2014139202 | 2014-07-04 | ||
| JP2014180097 | 2014-09-04 | ||
| JP2014-180097 | 2014-09-04 | ||
| JP2015-105353 | 2015-05-25 | ||
| JP2015105353 | 2015-05-25 | ||
| CN201580003223.6A CN105829371A (en) | 2014-07-04 | 2015-07-03 | Photocurable composition and method for manufacturing electronic component |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580003223.6A Division CN105829371A (en) | 2014-07-04 | 2015-07-03 | Photocurable composition and method for manufacturing electronic component |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110079196A true CN110079196A (en) | 2019-08-02 |
Family
ID=55019449
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580003223.6A Pending CN105829371A (en) | 2014-07-04 | 2015-07-03 | Photocurable composition and method for manufacturing electronic component |
| CN201811561851.8A Pending CN110079196A (en) | 2014-07-04 | 2015-07-03 | The manufacturing method of Photocurable composition and electronic component |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580003223.6A Pending CN105829371A (en) | 2014-07-04 | 2015-07-03 | Photocurable composition and method for manufacturing electronic component |
Country Status (5)
| Country | Link |
|---|---|
| JP (4) | JP5889491B1 (en) |
| KR (1) | KR20180002479A (en) |
| CN (2) | CN105829371A (en) |
| TW (1) | TWI682238B (en) |
| WO (1) | WO2016002923A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180099456A (en) * | 2015-12-28 | 2018-09-05 | 세키스이가가쿠 고교가부시키가이샤 | Photocurable composition and method for producing electronic component |
| EP3321331B1 (en) * | 2016-11-10 | 2020-10-21 | Agfa-Gevaert | Solder mask inkjet inks for manufacturing printed circuit boards |
| KR20200033791A (en) * | 2017-07-21 | 2020-03-30 | 세키스이가가쿠 고교가부시키가이샤 | Curable composition, electronic component and manufacturing method of electronic component |
| JP6646640B2 (en) * | 2017-11-16 | 2020-02-14 | 積水化学工業株式会社 | Non-developable resist photocurable composition and method for producing electronic component |
| JP6646641B2 (en) * | 2017-11-16 | 2020-02-14 | 積水化学工業株式会社 | Non-developable resist curable composition, printed wiring board and method for producing electronic component |
| JPWO2019098248A1 (en) * | 2017-11-16 | 2020-10-01 | 積水化学工業株式会社 | Method for manufacturing resist-curable composition, printed wiring board and electronic component |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5723261A (en) * | 1989-11-30 | 1998-03-03 | Tamura Kaken Co., Ltd. | Photopolymerizable composition |
| JP2007171246A (en) * | 2005-12-19 | 2007-07-05 | Fujifilm Corp | Photosensitive composition, pattern forming material, pattern forming apparatus and pattern forming method |
| JP2008211036A (en) * | 2007-02-27 | 2008-09-11 | Tamura Kaken Co Ltd | Photosensitive resin composition, solder resist composition for printed wiring board, and printed wiring board |
| JP2012004487A (en) * | 2010-06-21 | 2012-01-05 | Tamura Seisakusho Co Ltd | Solar cell back sheet |
| CN102520582A (en) * | 2010-08-18 | 2012-06-27 | 株式会社田村制作所 | White curable resin composition |
| JP2013194057A (en) * | 2012-03-15 | 2013-09-30 | Sanwa Kagaku Kogyo Kk | Composition for forming solder resist for led |
| JP5325805B2 (en) * | 2010-01-29 | 2013-10-23 | 株式会社タムラ製作所 | Photosensitive resin composition and printed wiring board using cured film thereof |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5819371A (en) * | 1981-07-25 | 1983-02-04 | Matsushita Electric Ind Co Ltd | Photo-setting resin composition for covering |
| JP3319621B2 (en) * | 1992-11-20 | 2002-09-03 | 日本化薬株式会社 | Epoxy (meth) acrylate, polymerizable resin composition and cured product thereof |
| JP2875747B2 (en) * | 1994-09-20 | 1999-03-31 | 四国化成工業株式会社 | Photocurable resin composition |
| JP4066706B2 (en) * | 2001-09-04 | 2008-03-26 | 凸版印刷株式会社 | Black pigment-containing active energy ray-curable composition and lenticular lens sheet using the same |
| JP2003221500A (en) * | 2002-01-31 | 2003-08-05 | Sumitomo Bakelite Co Ltd | Unsaturated polyester resin molding material |
| JP2007178450A (en) * | 2005-12-26 | 2007-07-12 | Fujifilm Corp | Pattern forming material and pattern forming method |
| JP2008304849A (en) * | 2007-06-11 | 2008-12-18 | Kaneka Corp | Photosensitive dry film resist, printed wiring board using same and method for producing printed wiring board |
| US8414981B2 (en) * | 2007-08-17 | 2013-04-09 | Prc Desoto International, Inc. | Multilayer coatings suitable for aerospace applications |
| KR101521362B1 (en) * | 2010-09-22 | 2015-05-18 | 세키스이가가쿠 고교가부시키가이샤 | Curable composition for inkjet, and method for producing electronic component |
| WO2012132423A1 (en) * | 2011-03-31 | 2012-10-04 | 太陽ホールディングス株式会社 | Photocurable/thermosetting inkjet composition, and printed wiring board using same |
| JP2012241096A (en) * | 2011-05-19 | 2012-12-10 | Nichiban Co Ltd | Ultraviolet curing type masking agent composition |
| JP6085938B2 (en) * | 2012-10-05 | 2017-03-01 | 唐沢 伸 | Luminescent guidance display board |
| JP6209365B2 (en) * | 2012-12-11 | 2017-10-04 | 太陽インキ製造株式会社 | Photocurable resin composition, solder resist and printed wiring board |
| US9490046B2 (en) * | 2013-05-23 | 2016-11-08 | Sekisui Chemical Co., Ltd. | Conductive material and connected structure |
| JP2015093419A (en) * | 2013-11-12 | 2015-05-18 | 日油株式会社 | Optical laminate |
| JP2015196765A (en) * | 2014-04-01 | 2015-11-09 | 東洋インキＳｃホールディングス株式会社 | Active energy ray-curable varnish composition and laminate of the same |
-
2015
- 2015-07-03 WO PCT/JP2015/069241 patent/WO2016002923A1/en active Application Filing
- 2015-07-03 JP JP2015533778A patent/JP5889491B1/en not_active Expired - Fee Related
- 2015-07-03 CN CN201580003223.6A patent/CN105829371A/en active Pending
- 2015-07-03 KR KR1020167016200A patent/KR20180002479A/en unknown
- 2015-07-03 TW TW104121754A patent/TWI682238B/en not_active IP Right Cessation
- 2015-07-03 CN CN201811561851.8A patent/CN110079196A/en active Pending
-
2016
- 2016-02-15 JP JP2016025777A patent/JP6523985B2/en not_active Expired - Fee Related
- 2016-02-15 JP JP2016025779A patent/JP2016204631A/en active Pending
- 2016-02-15 JP JP2016025778A patent/JP6523986B2/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5723261A (en) * | 1989-11-30 | 1998-03-03 | Tamura Kaken Co., Ltd. | Photopolymerizable composition |
| JP2007171246A (en) * | 2005-12-19 | 2007-07-05 | Fujifilm Corp | Photosensitive composition, pattern forming material, pattern forming apparatus and pattern forming method |
| JP2008211036A (en) * | 2007-02-27 | 2008-09-11 | Tamura Kaken Co Ltd | Photosensitive resin composition, solder resist composition for printed wiring board, and printed wiring board |
| JP5325805B2 (en) * | 2010-01-29 | 2013-10-23 | 株式会社タムラ製作所 | Photosensitive resin composition and printed wiring board using cured film thereof |
| JP2012004487A (en) * | 2010-06-21 | 2012-01-05 | Tamura Seisakusho Co Ltd | Solar cell back sheet |
| CN102520582A (en) * | 2010-08-18 | 2012-06-27 | 株式会社田村制作所 | White curable resin composition |
| JP2013194057A (en) * | 2012-03-15 | 2013-09-30 | Sanwa Kagaku Kogyo Kk | Composition for forming solder resist for led |
Non-Patent Citations (2)
| Title |
|---|
| ZHENGLONG YANG等: "Newly UV-curable polyurethane coatings prepared by multifunctional thiol- and ene-terminated polyurethane aqueous dispersions mixtures: Preparation and characterization", 《POLYMER》 * |
| 杨邦朝等: "《多芯片组件（MCM）技术及其应用》", 31 August 2001 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2016204631A (en) | 2016-12-08 |
| JP2016204629A (en) | 2016-12-08 |
| TW201606428A (en) | 2016-02-16 |
| JP6523986B2 (en) | 2019-06-05 |
| JP5889491B1 (en) | 2016-03-22 |
| KR20180002479A (en) | 2018-01-08 |
| JPWO2016002923A1 (en) | 2017-04-27 |
| TWI682238B (en) | 2020-01-11 |
| JP6523985B2 (en) | 2019-06-05 |
| WO2016002923A1 (en) | 2016-01-07 |
| JP2016204630A (en) | 2016-12-08 |
| CN105829371A (en) | 2016-08-03 |
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