TW201224663A - Photosensitive composition, photosensitive film, permanent pattern, method of forming a permanent pattern, and printed board - Google Patents

Abstract

The present invention provides a photosensitive composition, a photosensitive film made from the same, permanent pattern, method of forming a permanent pattern, and printed board, wherein the photosensitive composition contains an inorganic filler with a structure -L1 -NH-R 2 (L1 is C1 to 12 alkylene, R2 is C1 to 12 organic group), a binder, a photopolymerization initiator and a polymerizable compound. A content of the inorganic filler is 30 mass% relative to the total solid content.

Description

201224663 VI. [Technical Field] The present invention relates to a photosensitive composition suitable for a solder resist or the like, and a photosensitive film using the photosensitive composition, a high-definition permanent pattern (protective film, interlayer insulation) a film, a solder resist, etc., a permanent pattern forming method, and a printing substrate, and particularly a permanent pattern having excellent heat fatigue resistance for thermal history or temperature cycle test (TCT) used in a wiring substrate or an electronic component module, An efficient formation method, and a printed substrate having a permanent pattern formed by the formation method. [Prior Art] In recent years, electronic equipment has been required to be high-performance, high-performance, high-quality, and high-reliability, as small, thin, and lightweight, as represented by mobile communication devices. Moreover, the electronic component module mounted on such an electronic device is also required to be small and high in density. In recent years, in the surface of an insulating substrate made of a glass fiber and an epoxy resin which are lighter and more dense, 'a copper or gold having a low electric bismuth metal is used, and a film formation method is used. The so-called printed circuit board of the wiring conductor layer is used in an electronic component module. Further, the printing base plate is also changed toward the build-up wiring board which is more highly densely lined. Such a build-up wiring board is formed, for example, on an insulating substrate made of glass fiber and epoxy resin, and a film formed of a thermosetting resin is thermally cured to form an insulating layer, and then a carbon dioxide laser is used. An opening is bored therein, and then the surface of the insulating layer is chemically roughened, and an electroless iron steel method and an electrolytic copper plating method are used to form a copper film, and a conductor layer is formed in the opening while forming a wiring conductor layer on the surface of the insulating layer. It is produced by repeating the formation of such an insulating layer and a wiring conductor layer.

-3 · S 201224663 二导二::: On the surface of the substrate, in order to protect the insulating layer from being mismatched or rotted, and to prevent the installation of electrons on the wiring substrate, the adhesion is increased to π. A solder resist layer with a degree of 20 μm to 5 μm. The layer of the retardant agent is generally cross-linked by the soluble light; the adhesion between the layer and the insulating layer is good, and contains 5 mass% to 75 mass 4 and a flexible resin structure coefficient and insulation. Look at or match (4) machine filler to integrate the thermal expansion coefficient of the thermal expansion 4 wiring conductor layer. : Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ The wiring conductor layer inside is used as an electronic component module for a thousand V body device. Solder-like green τ Μ α The solder resist layer used in the electronic component module is 1 () 11 Ω ~ 1 () Ι 3 Ω. Then, in the general agent layer, the Jamen light and the resin are exposed by soldering and imaging. In the case of solder mask: /, in order to exhibit imaging properties, the solder resist layer contains, this 11 rebel Therefore, the water absorption rate 胄 'suddenly absorbs the moisture in the air. ・The knife will reduce the insulation resistance of the solder resist layer to less than Ω8Ω, and the two bodies will be short-circuited, and this moisture is a problem. The result is a semi-conductor that deteriorates the electrical reliability of the wiring substrate, and is printed on the BGA (ball grid array), (10) (wafer size package), etc., and is printed in an essential part by the infrared force cream solder. Solder the solder to fix it. In this step, the name is inside and outside: ζ丨, earth, . The arrival temperature is significantly as high as 220. (:~240. (:, because of the impact, the right side is in contact with ^/r 66 X, cracking occurs, there is a problem that the retractability (solder heat resistance) is reduced from the peeling of the substrate or the fixing material, and this is required. 201224663 "······························································································ The content of the body, the phase ', and not the general elastomer. Compared with 1 〇〇 by mass of the acidic epoxy resin and 4 of the unsaturation of the iron, this m must be 2 parts by mass to 30 The mass fraction. ..., and the special elastomer can improve the impact properties. The imaging properties of the unexposed portion of the agent are not charged: (Heat-resistant, in order to improve the imaging performance, there are proposals: Encapsulation of polyamines containing an enradyl group, and the presence of a base and an ethylenic acid and its + AT eight have a bad milk. Patent Document 2) " "Reactive elastomers (reference and pinch in order to improve heat resistance) Impact filler (TCT), electrical insulation (HAST), and right inorganic fillers such as barium sulfate Filling 詈 = coating liquid viscosity increase 'coating suitability is still insufficient, occurrence = : screen printing problem. Also, depending on the situation, in the preparation of the coating liquid, J.,, machine: filler dispersion In order to solve the problem that the inorganic filler cannot be dispersed, an insulating resin composition containing a thermosetting resin, an inorganic filler, and a polymer dispersing agent has been proposed (refer to Patent Document 3). However, it is not possible to prevent the aggregation of the inorganic filler from drying when the insulating resin composition is dried, and it is not possible to control the composition of the insulating resin. In the insulating resin composition, the optical resin does not easily pass through the insulating resin composition, and the optical curing of the insulating resin composition is difficult to pass. 201224663 Further, there is proposed an insulating resin composition containing a filler treated with a binder and a decane coupling agent (see Patent Document 4). # $ The filling amount of the filler in the photosensitive composition is as low as: mass% to 13 mass. When the filling amount is high, the inorganic filling is not dispersed, and since the inorganic filler has a large particle diameter, the insulating resin is present. The composition Φ, _ _ _ _ „ 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易A film (refer to Patent Document 5). ^ ^ The filling amount of the inorganic filler in the photosensitive composition is as low as 7 mass% to 8 mass%, and when the filling amount is further increased, the inorganic filler is dispersed. [PRIOR ART DOCUMENT] [Patent Document] [Patent Document 2] Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. [Patent Document 4] JP-A-2003-234439 [Patent Document 5] JP-A-2003030 No. 1 SUMMARY OF THE INVENTION The object of the present invention is to cope with the above problems and achieve the following objects. That is, the object of the present invention is to provide a cured film having excellent embedding property, thermal shock resistance (TCT), electrical insulating properties (HAST), solder heat resistance, and analytical properties, and to improve the photosensitive film. A photosensitive composition of a dispersibility of an inorganic filler, and a photosensitive film 'a permanent pattern, a permanent pattern forming method, and a printed substrate.

S 201224663 Further, the object of the present invention is to provide a high-performance cured film which is excellent in embedding property, thermal shock resistance (TCT), electrical insulating property (HAST), solder heat resistance, analytical property, and south light transmittance. Further, a photosensitive composition capable of improving the dispersibility of the inorganic filler in the photosensitive film, a photosensitive film, a permanent pattern, a permanent pattern forming method, and a printed substrate can be obtained. The means to solve the aforementioned problems are as follows. In other words, a photosensitive composition containing at least one of an inorganic filler, a binder, a photopolymerization initiator, and a polymerizable compound, wherein: the photosensitive composition is all: The content of the inorganic filler in the solid content is 30% by mass or more, and the surface of the inorganic filler has a partial structure represented by the following formula (A): • General formula (A) Organic group, L! Carbon_number - L!-NH-R? In the formula (A), 'R2 represents a 1 to 12 alkylene group having 1 to 12 carbon atoms. &lt; 2 &gt;&lt; 1 &gt; § A photosensitive composition comprising the inorganic filler having an average particle diameter (d50) of less than 0.3 μm. <3> The photosensitive composition according to <1> or <2>, wherein the surface of the particle of the inorganic filler has a partial structure '-si(〇R1)2-L represented by the following formula: , -NH-R2 · · · Formula (B) In the formula (B), 'R】 represents a methyl group or an ethyl group, and i represents an organic group of the carbon number 12, and 1 represents an alkylene group having a carbon number of 12 Here, the two heart systems can each be the same or different. 201224663 &lt;4&gt; such as any one of &lt;1:&gt;~&lt;3&gt; wherein the inorganic filler is treated by the following photosensitive agent, eight ( C) the formula (C) shown

NH-^CH2j—si—〇R

OR In the formula (C.), 'R represents a methyl group or an ethyl group, and here, each of the three feet may be the same or different. Further, it is not an integer of 1 to 5; as described in any one of <1> to <4>, wherein the inorganic filler is a vermiculite. The photosensitive composition &lt;6&gt; is a photosensitive composition having a pot of Φ - Γ, +, machine gw / D, and a resin having an ethylenically unsaturated group, such as any of &lt;1> And at least one resin selected from the group consisting of ♦ amine phthalic acid vinegar resin, yoghurt milk phase, month g, and polyamidamine or polyimide resin. <1> The photosensitive composition according to any one of <bKbt, wherein the binder contains g-penetrating resin; and the polyurethane resin having an ethylenic group and an ethylenically unsaturated group. The photosensitive composition according to any one of <1>, wherein the binder has a mass average molecular weight of 2, 〇〇〇~6〇, 〇〇〇, and an acid value. The polyurethane resin containing an acid group and an ethylenically unsaturated group is 20 mgKOH/g~l20 mgKOH/g, and the ethylenically unsaturated group equivalent is 0.05 mmol / g - 3.0 mmol / g. The photosensitive composition according to any one of <1>, wherein the binder is a polyamine A 201224663 acid ester resin containing an acid group and an ethylenically unsaturated group, and is on the side. The chain contains a compound represented by the following formula (at least one of the groups, ~(3))

Sulfurogen In the formula (1), R group, X represents an oxygen atom or a monovalent organic group

%小虱 atom or monovalent organic or -N(R12) money Here, R12 represents hydrogen Formula (2)

In the formula (2), r4 to r8 each independently represent a gas primordial group 'Y represents an oxygen atom, a sulfur atom or Ν(]112)_; here, ...: a disk' is synonymous with R12 of the general formula (1) , , month, J

In the formula (3), r9 to ri丨 each independently represent a hydrogen atom or an i-valent organic group. Two Z represents an oxygen atom, a sulfur atom, ... N(Rl3)_ or a phenyl group which may have a substituent. 'Here' Ri3 represents an alkyl group which may have a substituent. The photosensitive composition according to any one of the above-mentioned, wherein the binder is a polyamine formic acid containing an acid group and an ethylenically unsaturated group, and Partial structure shown by the following general formula (UG), 201224663 Formula (UG) Ο

II Ο rH O-C-NH-II /CH2 /

—NH—C-0 , CH

I Α, χ I,

II R3, C, R2 In the formula (UG), R1 to R3 each independently represent a hydrogen atom or a monovalent organic group, A represents a divalent organic residue, and X represents an oxygen atom, a sulfur atom or -NCR12)-; Wherein R12 represents a hydrogen atom or a monovalent organic group. The photosensitive composition according to any one of the above-mentioned <1>, wherein the binder is a polyamine phthalate resin containing an acid group and an ethylenically unsaturated group, and a reaction product of an isocyanate compound and at least two kinds of diol compounds, at least one of which is (1) has a ethylenically unsaturated group, and at least one of the hydroxyl groups is a diol compound of a secondary alcohol Further, at least one of (2) a diol compound having a carboxyl group. The photosensitive composition according to the above-mentioned item (1), wherein the diol compound having an ethylenically unsaturated group and at least one of the hydroxyl groups is a secondary alcohol is the following a compound of the formula (G), a formula (G) rn PH CH2 /

HO, CH

II , o〆, /1 201224663 In the general formula (G), R^-R3 each independently represents a hydrogen atom or a monovalent organic group, and A represents a divalent organic residue 'X represents an oxygen atom, a sulfur atom or _n ( R12)_; Here, R12 represents a hydrogen atom or a monovalent organic group. The photosensitive composition according to any one of <1>, further comprising a thermoplastic elastomer. The photosensitive composition described in <13>, wherein the thermoplastic elastomer system is a styrene elastomer, an olefin elastomer, an amine phthalate elastomer, a polyester elastomer, or a polyamine At least one elastomer selected from the group consisting of an elastomer, an acrylic elastomer, and a polyoxo elastomer. &lt;15&gt; The photosensitive film is characterized in that it has a photosensitive layer on the support, and the photosensitive layer is composed of the photosensitive composition of any one of &lt;1&gt; to &lt;14&gt;. &lt; 1 6 &gt; A photosensitive film comprising: a photosensitive layer formed of a photosensitive composition on a support, the photosensitive layer containing an inorganic filler, the particle surface of the inorganic filler having the following In the partial structure represented by the general formula (A), the content of the inorganic filler in all the solid components of the photosensitive composition is 30% by mass or more, and the photosensitive layer has a melt viscosity of 3×10 5 Pa·s or more at 3 〇t. And the photosensitive layer has a melt viscosity of 7 〇t: when the average particle diameter of the inorganic filler is less than 0.3 μm, the average particle diameter is 0.3 μm to be 5 1 03 P a · s or less, when the inorganic In the above case of the filler, it is 2x10 Pa·s or less, -Li-NH-R2 • · · Formula (A) In the formula (A), 'I represents an organic group having a carbon number of 丨~12, and ^ represents a carbon number. Alkyl. The photosensitive film according to <16>, wherein the inorganic filler has an average particle diameter (d50) of less than 0. 3 μm. The photosensitive film according to the <16>, wherein the photosensitive layer contains at least one of the inorganic filler described above, together with a binder, a photopolymerization initiator, and a polymerizable compound. The photosensitive film according to any one of the above-mentioned photosensitive compositions, wherein the content of the inorganic filler in the solid content of the photosensitive composition is 50% by mass or more. The photosensitive film of any one of the above-mentioned inorganic fillers has a partial structure represented by the following general formula (Β), -Si(〇), in the photosensitive film described in any one of the above-mentioned <16>. R1) 2_L1-NH-R2 · · • Formula (B) In the formula (B), R] represents a fluorenyl group or an ethyl group, and the rule 2 represents an organic group of a carbon number ' 1^ represents a carbon number ι 12 Alkyl; here, two 1^ can each be the same or different. The photosensitive film described in any one of <16> to <20> wherein the inorganic filler is subjected to the following formula (the 矽焓 视 所 所 所 所 所 所Treated by mixture, formula (C)

In the formula (C), 'R represents a methyl group or an ethyl group, and η represents a group of W. Each of the three R groups may be the same or different. The amine, such as the photosensitive material of any one of &lt;16&gt; to &lt;21&gt;, and the above-mentioned inorganic filler-based vermiculite.

S -12-201224663 &lt; 23> The photosensitive film described in the above-mentioned item, wherein the seven-part binder is a resin containing an acid group and an ethylenically unsaturated group, Further, it is at least one selected from the group consisting of polyamine phthalate resins, epoxy resins, and polyamidamine or polyimide resins. The photosensitive film according to any one of the above-mentioned items, wherein the binder is a polyamine formic acid containing resin having an acid group or an ethylenically unsaturated group. The photo-sensitive film of any one of the above-mentioned binders has a mass average molecular weight of 2, 〇〇〇~6 0,0 0 0, and an acid. The urethane resin having an acid group and an ethylenically unsaturated group having a valence of 20 mgKOH/g to 120 mgKOH/g and an ethylenically unsaturated group equivalent of 0.05111111〇1/§3, 〇111111〇1/§. &lt;26&gt; The photosensitive film of any one of &lt;18&gt;~&lt;25&gt;, wherein the above-mentioned binder contains an acid group and an ethylenically unsaturated group of a polyamine f-resin resin and is in a side chain Containing at least one of the functional groups represented by the following general formulae (1) to (3),

The general formula (1) or the monovalent organic R12 represents a hydrogen in the formula (1), and rLr3 each independently represents a hydrogen atom group 'X represents an oxygen atom, a sulfur atom or -NCR12)-; here, an atom or a monovalent organic group ,

General formula (2)

S -13- 201224663 In the formula u), R and R8 each independently represent a hydrogen atom or a certain γ group, γ class + ^ ^ "hole atom 'sulfone atom or -N(R12)_; here, R is 2 Synonymous with R12 of the general formula (1), &gt;, 1

In the formula (3), R9 to R11 each independently represent a hydrogen atom or a monovalent organic group on which Z represents an anthracene atom, a sulfur atom, -N(R13)- or a benzene having a substituent. And 胄, Rl3 represents an alkyl group which may have a substituent. &lt; 2 7 wherein the photosensitive thinness q@V· X r* and the binder are acid group-containing and ethylenically unsaturated group according to any one of the above-mentioned items. a polyurethane resin, bis[alpha], and having a partial structure represented by the following formula (UG), formula (UG)

In the general formula (UG), the mechanical group, Α indicates that 2俨'~R3 each independently represents a hydrogen atom or a monovalent has -N(R12), and here the R1 machine residue 'X represents an oxygen atom' sulfur atom Or &lt;28&gt; represents a hydrogen atom or a monovalent organic group. The film of the above-mentioned:=:&lt;27&gt;, wherein the photosensitive isocyanate resin according to any one of the above-mentioned items, and the polyamine-based isocyanate compound containing an acid group and an ethylenically unsaturated group, and at least two kinds of alcohol

-14- S 201224663 The reaction product of the compound, at least one of the at least two diol compounds (1) having an ethylenically unsaturated group, and at least one of the diol compounds having at least one of the secondary alcohols A diol compound having a carboxyl group (7). <29> The photosensitive film according to <28>, wherein (1) has a ethylenically unsaturated group, and at least one of the base group is a secondary alcohol diol compound, which is as follows a compound of the formula (G), a formula (G) /CH2

HO, CH

I 〇, c, c, r1

II R3〆. 2 In the general formula (G), Ri to r3 each independently represent a hydrogen atom or a methicone, A represents a divalent organic residue, X represents an oxygen atom, a sulfur atom or 'here' R12 represents a hydrogen atom or a valence Organic base. The film according to any one of <16> to <29&gt;, further comprising a thermoplastic elastomer. Thin film &lt;31&gt; The photosensitive film described in <30>, wherein the above-mentioned elastic system is composed of a styrene-based elastomer, an olefin-based elastomer, ",, d ^ formate carboxylic acid elastomer, polyester At least one elastic $acid selected from the group consisting of an elastomer, a polyamine elastomer, a silicone elastomer, and a polyoxynene elastomer, and a permanent pattern forming method, characterized in that the above &gt; The photosensitive composition according to any one of the above-mentioned items, which is applied to &lt;1 φ, the surface of the steroid, is dried, and the photosensitive layer is laminated to form a layered body, and then the operation is exposed to 201224663 &lt;33&gt; - Permanent pattern 荦 ^ is characterized by a pre-loaded water-long pattern forming method. &lt; 34 &gt; - a kind of printed substrate, complex ^ "Specially formed by the pre-loaded Shoujiu case The method forms a permanent pattern. According to the present invention, it is possible to obtain a high-performance cured film having excellent embedding property, | (TCT), electrical insulating properties (HAST), } ~ tin heat resistance and light-dissolving property, and can improve dispersion of a photosensitive filler. A photosensitive composition, a permanent pattern, a permanent pattern forming method, and a printed substrate. The features and advantages of the present invention are known. [Embodiment] [Form of the invention] (Photosensitive composition) The photosensitive composition of the present invention contains at least one kind of d, and particularly preferably contains a photopolymerization initiating compound of each binder, and contains a thermal crosslinking agent. , organic solvent, heat, heat hardening accelerator, coloring agent, adhesion promoter, heat, and other components as needed. In the present specification, the content "photosensitive component content" is a content (solid content) of a specified solid substance which means all of the photosensitive composition. &lt;Inorganic filler&gt; The surface of the particles of the inorganic filler (inorganic filler) used in the present invention has a partial structure represented by the following formula (A) &lt;3 2 &gt; description &lt; 3 2 &gt; The thermal shock resistance, the matte film in the high-transparent film, the inorganic filler described below, and the solid-state component in the polymerizable plastic elastomer polymerization inhibitor are fillers. Furthermore, it is preferable that the surface of the particle is preferably bonded to the surface of the filler particle, preferably partially containing the group of the formula (A) (the entire group may be monovalent) Any of the ~3 valences is chemically bonded to a group (for example, a via group) present on the surface of the particles of the filler. -L1-NH-R2 In the formula (A), a stretching group of 1 to 12 is used. • The general formula (A) I represents an organic group having a carbon number of 1 to 12, and represents a carbon number. The partial structure represented by the above formula (A) is preferably a partial structure represented by the following formula (B). On the surface of the particles of the filler, there is (preferably 1 bonded to the surface of the particle surface). • General formula (Β) ' R2 represents a carbon number of 1 to 12, and 2 each may be -Si(〇R1)2.Ll.NH.R2 · · In the formula (B), '1^ represents a methyl group or Ethyl organic group, h represents an alkyl group of a carbon number; the same or different. The inorganic filler having the structure of the above-described formula (A) or (B) on the surface of the particle of the filler can be treated by a decane coupling agent represented by the following formula (BA), that is, by The particles are stored on the surface

dOhSi-LrNH In the formula (BA), 'Rl represents a methyl group or an ethyl group, I represents an organic group having a carbon number of 1 to u, and L1 represents a carbon number 丨~丨? The alkyl group; here, the three sizes are the same or different. Among the decane coupling agents represented by the above formula (BA), a mixture of the formula (9) is preferred. For the next fan 201224663 general formula (c)

OR

OR In the general formula (C), 'R represents an integer ·, , ^ . y T group or an ethyl group, and η represents a positive number of 1 to 5, and here, 3 may each be the same or different. The money coupling agent represented by the formula (c) is, for example, &lt;&gt; The compound (10) m_5 and the like shown in the configuration. /^x , x 〇ch3 leaf life 〇 〇 ch3 och3 The decane coupling agent represented by the general formula (BA) is preferably a mass of 01 to 50 with respect to the inorganic filling of 0 00 gram parts. The portion is more preferably • 10 parts by mass, and more preferably 0.1 to 5 parts by mass of the surface treatment. Further, whether the surface of the inorganic filler has a general formula or (none part of the gentleman γτι, · '. The formula can be used, for example, by using ESCA (PHI1 800, uivac-Phi-iiJ \ _ * x , 'In the invention, the inorganic filler is preferably acidic, 'the surface of the particle is ', UU 〇A/c 丄^, especially, the surface of the particle is 'acidic inorganic The filler is not a ruthenium atom: the system can be appropriately selected according to the purpose, and examples thereof include an inorganic filler containing a field-constituting atom (aragonite, talc) and a group of 钡原+^^3, although An inorganic filler (such as barium sulfate) constituting an atom, preferably S has a broken atom as an inorganic filler constituting an atom. In addition, the inorganic filler is a heat-curing property of a cured film containing a ruthenium atom as a photosensitive composition constituting the atomic core, and at the same time, it is excellent in adhesion to an acid group and an ethylenic unsaturated group described later. of

S 18 - 201224663 The dispersibility of the urethane s-resin is improved. The degree of the photosensitive composition can be kept within an appropriate range to obtain suitable coating suitability. ▲ Inorganic filler containing a ruthenium atom as a constituent atom, in the present invention: preferably vermiculite (aragonite particle). Examples of the vermiculite include "phase/stone", crystalline vermiculite, and molten vermiculite. The average particle diameter (d50) of the inorganic filler used in the present invention is preferably 3·0 μηι or less (preferably 1 〇 nm to 3 〇μιη), more preferably 2 祚 below the claw (k is 70 nm to 2.5 μηη) ). In particular, when the average particle diameter of the inorganic filler is less than 0.3 μm, it is preferable because it is excellent in light transmittance. When it is such a fine particle, it is preferably lOnm or more and less than 〇.3μηη, more preferably 〇nm~25〇nm, and particularly preferably 70nrn to 150nm. In addition, when the average particle diameter exceeds 3·0 μη, the smoothness cannot be maintained. On the other hand, if the average particle diameter (d50) is within the above preferred range, the coating viscosity and the smoothness or heat resistance of the cured film are applied. The point of sex is also beneficial. The average particle size (d 5 0) of the inorganic filler is defined as the cumulative value of 50% when defined as the cumulative (cumulative) mass percentage, defined as d50 (D5〇). For example, a dynamic light scattering photometer (trade name: DLS7000, manufactured by Otsuka Electronics Co., Ltd.) can be used, and the measurement principle is a dynamic light scattering method, and the size distribution analysis method is used for the cumulative method and/or the histogram method. The I' of the inorganic filler in all the solid components of the photosensitive composition is 30% by mass or more (preferably 3 Å by mass) in the present invention.

S -19- 201224663 %, more preferably 3 〇 quality 0 / 〇 ~ 7 5 quality, , / / 〇) 'Chef Jia is 3 5 quality | 〇 / LV w is preferably 35 mass% ~ 8 〇 quality Berry / 〇 above (the 0 is better than 35 mass% ~ 75 and 曰. /,, more preferably 40% by mass or more (better Becha / 〇) (early and good for 4 〇 mass% ~ 80 quality Jin ο / , is 40% by mass to 75 mass 0, 罝〆〇 'better 0 / ' is preferably 50 mass. / ° (preferably 50 dan) "% by mass, more preferably 5. Quality. %~75质量%). It is 5. Berry This solid content name: Θ Less than 30 Berry% 'The CT resistance will change to more than 80% by mass, and the viscosity of the film will increase -:: Poor: It is advantageous if the solid content is in the above preferred range = 彳 * Analytical &lt; Stretching agent &gt; As a binder, there is no particular limitation. It can be suitably used according to the purpose: it is preferably a resin containing an acid group and an ethylenically unsaturated group. The acid amine ge 曰 可 can be exemplified by polyurethane resin, epoxy resin, poly-hard or poly Imine resin. ΐ 'The so-called ethyl sulphate unsaturated base, which has the base of the banned bond that is consumed by the immigrants or the sufficiency' is not an aromatic ground-based ethylenic unsaturated group such as benzene. In the present invention, the epoxy resin is not a resin having a ring or a second resin, but is a resin plate which is formed by reacting an epoxy group with an epoxy resin as described later. Among the resins containing an acid group and an ethylenically unsaturated group, the above-mentioned polyurethane resin and epoxy resin are particularly preferably polyamine-based vinegar resins. A carboxyl group, a sulfo group, a diphosphoryl group or the like is obtained, but in the present invention, a carboxyl group is particularly preferred.

-20 S 201224663 ) Polyurethane resin - a saturated polyurethane resin, which is suitably selected, preferably in which ruthenium is substituted by an atom which constitutes a main chain of the polyurethane resin. The unsaturation bond, that is, the polyurethane resin and the bond obtained by reacting this or an ethylenically unsaturated group directly by the hoch2ch=chch2oh reaction. Furthermore, since the blocked portion of the vinyl-containing end is not a side unsaturated bond, (i) by having an ethylenically unsaturated group in the two, and (ii) a carboxyl group-containing polyuric acid and ethylene The polyurethane resin of the unsaturated group compound, also known as the polyurethane resin obtained by the polymerization method, also has an ethylenically unsaturated polyurethane resin (i) and (ii) in the side chain. - Acid-containing group and ethylenically unsaturated group white as the acid group and the ethyl group are not particularly limited, and may have an ethylenic unsaturated bond according to a side chain. Here, the so-called side chain is used as the main chain. The chain of atoms or the chain in which it is called 'the so-called side chain has an ethylene side bond containing an ethylenically unsaturated group, and the atom of the main chain is substituted. For example, a diol and 〇CN(CH2)6NC〇 are a compound containing a ethylenically unsaturated unsaturated group in the main chain, and a poly bond. A method obtained by introducing a polymerization reaction of an ethylene-type dissociated acid vinegar compound or a glycolated octa compound into a side chain, and reacting with an epoxy group in a molecule. Hereinafter, the urethane resin (i) obtained by the method (1), and the group (ii) will be referred to as a polyamine methyl s resin. The double-bonded polyurethane resin contains both. In the present invention, it is preferred that the obtained polyurethane resin-21-201224663-polyamine phthalate resin (i)- as the polyamine phthalate resin (i) does not have ▲ 'also It is suitably selected for the purpose of the specific limitation, and for example, at least one of the functional groups represented by *(1) to (3) in the side chain may be mentioned. The following formula 0 R3 P=C R1 R2

II General formula (1). The substituted group of the aryl group, the alkoxy group, the amine, and the gland group are also R1, in the R2 and the carbonyl group, the substituted aryl group, the dilute alkoxy group, the amine group, A substituent group of an anthracene or an aryl group, an amine group, a hydrazine group, or a methyl group thereof. a further group, an alkoxy group, or a group having a substituted substituent, and examples of the monovalent organic group include a halogen atom, a group, a cycloalkyl group, a cycloalkenyl group, an aryl group, a heterocyclic group, and an alkylthio group. Arylthio, amine, alkylamino, aryl, aryl amine, alkyl or arylsulfonyl, alkyl, oxycarbonyl, aryloxycarbonyl, decyl, decyloxy sulfhydryl, hydroxy, The radicals such as a mercapto group, a cyano group, a nitro group, a carboxylic acid group, a urethane group, and the like may be further referred to as the following ones. . It is preferably a hydrogen atom or an alkyl group which may have a substituent. The point where the radical reactivity is high, more preferably a hydrogen atom, R is preferably a hydrogen atom, a halogen atom, an amine group, a carboxyl yellow group, a nitro group, a cyano group, an alkyl group which may have a substituent, and an aryl group. Alkoxy group having a substituent, an oxy group, an alkylamino group which may have a substituent, may have

S • 22- 201224663 An arylamino group, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, etc., among which a radical is highly reactive, more preferably hydrogen An atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent. X represents an oxygen atom, a sulfur atom or -N(R12). Here, r12 represents a gas atom or a monovalent organic group, and π is preferably an alkyl group which may have a substituent, wherein the radical reactivity is high. The black is preferably a hydrogen atom, a methyl group, an ethyl group or an isopropyl group. Here, examples of the substituent in the group which may have a substituent include the i-valent organic group in the above R] to R3. The group is preferably an alkyl group, an alkenyl group, a fast group H alkoxy group, an oxy group, a self atom, an amine group, an alkylamino group, an arylamino group, a carboxyl group, an alkoxycarbonyl 'sulfo group, a nitro group'. Cyanogen, amidino, alkylsulfonyl, arylsulfonyl. R4 R8

I I - Y - C - c = c R5 R6 R7 Formula (2) In the formula (2), R4 to R8 each independently represent a hydrogen atom or a divalent organic group. The monovalent organic group in R to R8 is exemplified by the monovalent organic group in the above ri to R3. R4 to R8 are preferably a hydrogen atom, a dentate atom, an amine group or a monoalkylamino group. , a group, a oxy group, a nitro group, an aryl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, and an aromatic group which may have a substituent An oxy group, an azide group which may have a substituent, an arylamine group which may have a substituent, a sulfosulfonyl group which may have a substituent, an aryl fluorenyl group which may have a substituent, wherein the radical is highly reactive The point 'is more preferably a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, or an aryl group which may have a substituent. In the case of the substituent in the group which may have a substituent, the group exemplified as the i-valent organic group in the above R1 to R3 is exemplified. Further, γ represents an oxygen atom, a sulfur atom or -N (R'. Here, R15 is synonymous with r12 of the general formula (1). The preferred range and specific examples are the same. R11 ~ z - c = c R9 R10 (3) In the general formula (3), R to R11 each independently represent a hydrogen atom or an i-valent organic group. Examples of the organic group in R9 to R11 include the above-mentioned organic group in R1 to R3. R9 is preferably a hydrogen atom or an alkyl group which may have a substituent, and more preferably a hydrogen atom or a mercapto group at a point where the radical reactivity is high. R10 and R11 are preferably a hydrogen atom or a halogen atom amine group. a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, may have a substituent An aryloxy group, an alkylamino group which may have a substituent, an arylamine group which may have a substituent, an alkylsulfonyl group which may have a substituent, an aryl group which may have a substituent, wherein a radical reaction The point of highness is more preferably a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, or an aryl group which may have a substituent. Examples of the substituent in the group which may have a substituent include the groups exemplified as the monovalent organic group in the above R1 to R3. Further, Z represents an oxygen atom, a sulfur atom, -N(R13)- or may have a substituent. Further, R 3 is preferably an alkyl group which may have a substituent, and more preferably a thiol group, an ethyl group or an iso-propyl group at a point where the radical reactivity is high.

S-24- 201224663 A reaction of at least one of at least one of the polyurethane resin compounds to form a polyurethane resin. The structure unit represented by the diisocyanate type represented by the following general formula (4) and the diol compound represented by the general formula (5) is regarded as the basic skeleton OCN-X. °-NC〇, leather-V..., general formula (4) h〇-y°-oh, s bucket formula (5) In formulas (4) and (5), Ώ L main _ ^ in and independently A divalent organic residue. The above-mentioned precautions. The two isogasifications of K., the substance, or the diolation of the above formula (5). ^ ^ 匕. At least one of the above formula (1) to (3, at least one of the groups of the above formula (1) to (3), the introduction of the above formula _ 1 to 3) The base polyurethane resin shown as a reaction product of the t-diisocyanate compound and the diol compound. If this kind of large and soil method is used, the side chain of the celebrity is taken after the reaction of the polyurethane resin is formed, and it is easier to manufacture the side chain introduced with the above-mentioned 弋(1)(3). A base of polyamine phthalate resin.

The diisocyanate compound represented by the above formula (4) is not particularly limited-rJ, and may be appropriately selected according to the purpose, and examples thereof include a compound of a trisodium sulfonate and an amidine compound. A product obtained by an addition reaction with one equivalent of a monofunctional alcohol or a monofunctional amine compound having an unsaturated group. The seven-islet triisocyanate compound is not particularly limited, and is preferably selected for the purpose, and examples thereof include the compounds described in paragraphs "0034" to "〇〇35" of JP-A-2005-250438A. . The early functional alcohol having an unsaturated group or the aforementioned monofunctional amine Λ/, 〇' is not particularly limited, and may be appropriately selected according to the purpose, and for example, the paragraph "0" of JP-A-2005-250438 Compounds such as those described in "37". 201224663 Here, the method of introducing an unsaturated group into the side chain of the polyaminophthalic acid resin is not particularly limited, and may be appropriately selected according to the purpose, but is preferably used as a raw material for producing a polyurethane resin. A method of using a diisocyanate compound having an unsaturated group in a side chain. The diisocyanate compound is not particularly limited, and may be appropriately selected according to the purpose, and may be obtained by subjecting a triisocyanate compound to an equivalent amount of a monofunctional alcohol or a monofunctional amine compound having an unsaturated group. The diisocyanate compound is, for example, a compound having an unsaturated group in a side chain described in paragraphs "0042" to "0049" of JP-A-2005-250438. The polyamine phthalate resin (i) may be one other than the above-mentioned unsaturated group-containing diisocyanate compound from the viewpoint of improving the compatibility with other components in the polymerizable composition and improving storage stability. The isocyanate compound is copolymerized. The diisocyanate compound to be copolymerized is not particularly limited and may be appropriately selected according to the purpose, for example, a diisocyanate compound represented by the following formula (6). OCN-L^NCO Formula (6) In the formula (6), L1 represents a divalent aliphatic or aromatic hydrocarbon group which may have a substituent. L1 may also have other functional groups which do not react with isocyanate groups, such as esters, urethane carboxylic acid, acid amines, urea groups, as needed. The diisocyanate compound represented by the above formula (6) is not particularly limited and may be appropriately selected according to the purpose, and examples thereof include, for example, 2,4-nonylbenzene diisocyanate and 2,4-nonylbenzene diisocyanate. Dimer, 2,6-nonyl diisocyanate, p-phenylenediyl diisocyanate, m-benzodiazepine t=l 5 -26- 201224663 hexamethylene isocyanate • 2, 4 (or fat a cyclic antimony benzene alcohol and a diisocyanate trans-diisocyanate, 4,4,-diphenylmethane diisocyanate, hydrazine, 5- cyanate, 3,3'-dimethylbiphenyl-4, Diisocyanate S such as 4,-diisocyanate, compound '/, fluorenyl-isocyanate, trimethyl decyl diisocyanate, leucine diisocyanate, dimer acid diester, etc. Cyanate vinegar compound; isophorone diiso, 4,4'-decylene bis(cyclohexyl isocyanate), methylcyclohexanthene 2,6) diisocyanate, 1,3-(isocyanate fluorenyl) cyclohexane a diisocyanate compound such as an alkane; an addition product of 1 mole of butanediol and 2 molar diisocyanate, etc. - a diisocyanate compound . The above-mentioned limitation can be suitably selected from commercially available products, as well as alcohol compounds, in accordance with the phthalic acid ester resin of the pharmaceutically acceptable unsaturated group and the diolation unsaturated group. And isocyanate, the reaction is easy to prepare the unsaturated group of the two, the purpose of the general formula (5) is suitable for the purpose of selecting the compound, and the polyamine method, in addition to the previously produced raw material 'combination method . The alcohol compound may, for example, be a compound such as a halogenated diol compound and a compound containing an alcohol, an amine or a thiol. The alcohol compound, and the bis-alcohol compound&gt; can be exemplified by the method of the carbonate diol phthalic acid @1 resin, which is also used in the side chain as the above-mentioned side without any particular limitation of the methyl propylate compound\ The carboxylic acid group halogenation of the alcohol-unsaturated group is not particularly limited as described above, and there is no particular condensed diol compound or the like. The side chain is introduced into the ethylene as a polyamine, and the ethylenic unsaturated chain has an ethylenic property. The chain of the monoaldoyl group, the aminodiacid, and the ruthenium compound can be made into a vinyl group. It may be a diisocyanate compound (preferably a compound represented by the above-mentioned "2 (6)) and an ethylenically unsaturated group, and a hydroxyl group, in accordance with the above-mentioned item 5-27-201224663 弋(4) or a levy. At least one of the diol compounds of the secondary alcohol (preferably having an ethylenic acid group - at least one of which is a secondary alcohol, and the other is a diol compound of the '' and alcohol) More preferably, it is a reactive organism of the above diisocyanate compound and two kinds of diol compounds, one of the diol compounds is the above diol compound having an ethylenically unsaturated group, and the remaining one is a carboxyl group. A reactive organism of an alcohol compound. The diol compound having an ethylenically unsaturated group in the side chain is exemplified by the compounds described in the paragraphs "〇〇57" to "〇〇60" of JP-A-2005-21〇438. The compound described in the paragraphs "〇〇64" to "〇〇66" of JP-A-2005-250438, which is shown by the formula (G). Among these, it is preferably a compound of the paragraph "0064" to "〇〇66 J Τ δ", which is represented by the following general formula (G).

In the general formula (G), R1 to R3 each independently represent a hydrogen atom or a valence organic group 'A represents a divalent organic residue 'X represents an oxygen atom, a sulfur atom or _n(r12). Here, R12 represents a hydrogen atom or a monovalent organic group. -28- 1 201224663 Further, R1 to R3&amp;x in the above formula (G) are synonymous with R1 to R3 and X in the above formula (1), and preferred embodiments are also the same. It is considered that by using the polyurethane resin derived from the diol compound represented by the above formula (G), it is possible to effectively suppress excess molecules of the polymer main chain caused by secondary alcohol having a large steric hindrance. Exercise, and the strength of the film of the layer is increased. Here, the polyurethane resin derived from the diol compound represented by the formula (G) has a partial structure represented by the following formula (UG). General formula (UG) 〇 —NH - C~〇/CH2'

Ο II C—NH- , CH

In the formula (UG), R1 to R3 each independently represent a hydrogen atom or an i-valent organic group, A represents a divalent organic residue, and X represents an oxygen atom, a sulfur atom or 'R12:-', here, represents a hydrogen atom or The price is organic. R1 to R3, VIII and in the formula (g) are synonymous with r1 to r3, VIII and symmetry in the formula (G), and the preferred ranges are also the same. The polyamine phthalate resin γ having an ethylenically unsaturated bond in the side chain can be used in the side chain, for example, from the viewpoint of improving compatibility with other components in the polymerizable composition, and improving storage stability. The diol compound containing ethylene + # group is preferably selected according to the following, and the diol compound other than the diol compound containing an ethylenically unsaturated group in the side chain is not particularly limited, and may be appropriately selected according to the purpose, for example, A diol compound, a poly diol compound, a tartrate diol compound, and the like are condensed. These are diol compounds which do not contain an ethylenically unsaturated group or a carboxyl group as described later in the side chain. The diol compound other than the diol compound containing an ethylenically unsaturated group in the side chain is preferably represented by the following formula (u), and if it is incorporated as a polyamine phthalate resin, it has the following formula (u) The partial construction shown is incorporated. General formula (u)

HO—LU1—OH General formula (U1) 〇〇—NHC—0—Lu1-0—CNH— In the general formulae (U) and (U 1), LU1 indicates that the side chain does not contain ethylenically unsaturated groups and A divalent linking group of a carboxyl group. The LU1 may, for example, be an alkylene group, an aryl group or a divalent heterocyclic group, and the exudyl group may also contain -〇·, -OCOO·, phenylene, carbon-carbon double bonds in the chain of the stretching base. , carbon-carbon triple bond, -OCO-Z^COOJZ1 represents exudyl, extended alkenyl, and extended aryl). LU1 in the above formula (U) '(U1) is preferably _(CH2CH20)nulC H2CH2-, -[CH2CH(CH3)0]nul-CH2CH(CH3)-, -(CH2CH2C H20)nu, -CH2CH2CH2- ^ -[(CH2)nU2-〇C( = 〇)-(CH2)nU3-C( = 〇)0]nU4-0(CH2)nU2- or -[(CH2)nU5-0C( = 0)0] Nu6-(CH2) nu7-. Here, nul to nU7 each independently represent a number of 1 or more.

S -30- 201224663 In addition, the diol shown in the other two is used as the paragraph according to the purpose as N 〇. 1 in the paragraph according to the purpose, and can be used according to No. 9~No. The isocyanate is not a compound, and for example, the carboxylate resin may have a carboxyl group, and for example, the above-mentioned side chain contains an ethylenic alcohol compound, and is preferably a compound of the following formula (IIM compound). The above-mentioned poly-glycol diol compound is not particularly limited, and may be appropriately selected, and examples thereof include compounds described in JP-A-2005-250438, "0068" to "〇〇76". The above-mentioned polyglycol diol compound is not particularly limited, and may be appropriately selected, and examples thereof include "0077" to "〇〇79" and "〇〇83" of the special opening 2〇〇5·25〇438. ~ "〇〇85" ~ Νο·8 and Νο·13~Ν〇·18 described compounds. The polycarbonate diol compound is appropriately selected without particular limitation, and examples thereof include compounds described in paragraphs "0080" to "008 1" of JP-A-2005-250438 and paragraphs 12 of 〇〇84. Wait. In the synthesis of polyamine having an ethylenically unsaturated bond in the side chain, in addition to the above diol compound, a diol compound having a substituent reactive with an acid ester group may be used in combination. The diol having a substituent which does not react with an isocyanate group is not particularly limited, and can be appropriately selected according to the purpose, and the paragraph "〇〇8 7" of the Japanese Patent Publication No. 2 0.0 5 - 2 5 0 4 3 8 In the synthesis of the polyamine which has an ethylenically unsaturated bond in the side chain, the diol compound may be used in addition to the above diol compound. The diol compound having a carboxyl group as described above contains the following Those represented by the general formulae (17) to (19).

S -31- 201224663 R15 9 A A__ 10

HO - L3 - (p-L10-OH ICOOH formula (17)

HO-L9-r-r-L10-〇H General formula (18)

COOH HO-L9. N-L1

—OH General formula (19)

COOH In the general formulae (17) to (19), Ri1 represents a hydrogen atom and may have a substituent (for example, a dentate atom containing a cyano group, a nitro group, a _F, a _C1, a Βγ, a heart, or the like, _C〇NH2). An alkane of _c〇OR16, -OR16, _nhCONHR16, -NHCOOR16, -NHCOR16, -OCONHR16 (here, Ru represents an alkyl group having 1 to 10 carbon atoms or an aralkyl group having 7 to 15 carbon atoms) The base 'aralkyl group, aryl group, alkoxy group and aryloxy group are not particularly limited: they may be appropriately selected according to the purpose, and are preferably a hydrogen atom, a carbon number of 丨8 or less, and a carbon number of 6. ~15 aryl groups. In the above formulae (17) to (19), each of LWi may be the same or different, and may be a single bond or a substituent (for example, a leuco group, an aryl group, an aryl group, an oxo group, or a chain). There is no particular limitation on the divalent aliphatic or aromatic heart of the prime atom. 'It can be appropriately selected according to the purpose, and it is preferably a carbon number (four) extension base, and a number 6 to 15 extension. The base is better for the carbon number b. Further, as needed, in the above L9~L丨1, the γ * field G ^ _ may also have other functional groups which do not react with the isocyanate group, such as a few groups, a vine group, a urethane base, 醯-32, 1 201224663 Amino, ureido, ether. Further, two or three of the above R15, L9, L10, and L&quot; may form a ring. In the above formula (18), 'Ar is not particularly limited as long as it means a trivalent samarium containing a substituent, and may be appropriately selected according to the purpose, and preferably has a carbon number of 6 to 15 Family base. The diol compound having a carboxyl group represented by the above formulas (17) to (19) is not particularly limited and may be appropriately selected according to the purpose, and examples thereof include 3,5-dihydroxybenzoic acid and 2, 2-bis(hydroxyindenyl)propionic acid, 2,2-bis(2.ethyl)propionic acid, 2,2-bis(3-hydroxypropyl)propionic acid, bis(hydroxymethyl) vinegar, Bis(4-hydroxyphenyl)acetic acid, 2,2-bis(hydroxyindenyl)butyric acid, 4,4-bis(4-hydroxyphenyl)pentanoic acid, tartaric acid, hydrazine, hydrazine-dihydroxyethylglycine , N, N-bis(2-海ethyl)-3-carboxy-propionamide, and the like. By virtue of the presence of such a mercapto group, it is preferred to impart a property such as chlorine bondability and solubility to the polyurethane resin. Further, in the case of a polyurethane having an ethylenically unsaturated bond in a side chain, in addition to the above diol compound, a compound in which a tetracarboxylic dianhydride is opened by a diol compound may be used in combination. The compound which is a ring-opening of the tetracarboxylic dianhydride by the diol compound is not particularly limited, and may be appropriately selected according to the purpose. For example, the paragraph "〇〇95" of JP-A-2005-250438 is exemplified. The compound described in "〇1〇1". The polyaminophthalic acid ester resin having an ethylenically unsaturated bond in the side chain is obtained by adding the above-mentioned diisocyanate compound and the diol compound to an aprotic solvent to add a known touch corresponding to the activity of each reactivity. The medium is synthesized by heating. The diisocyanate and the di-33- &quot; alcohol or amine having an ethylenically unsaturated group may be used for the synthesis. Specifically, it is suitable that the molar ratio (Ma:Mb) of the alcohol compound of the exemplified compound 201224663 which is exemplified as the ethylenically unsaturated monofunctional alcohol or the monofunctional amine compound is not particularly suitable. Choice, the limit of comparison, 彳, 17 with early 乂 为 1:1~1.2:1, and the mountain ^ to deal with, the molecular dan 赤 私 ώ 猎 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇 醇It is synthesized in the form in which the heterogeneous 曰 曰 group does not remain. The acid is as described above having a saturated bond in the side chain: suitably used at the end of the polymer, in the main chain; at the end of the polymer: at the end of the polymer, the primary bond has an unsaturated group, and the second substance has an ethylenicity in the side chain. Between the polyamine resins with saturated bonds, the polyamines with a bovine unsaturated bond improve the reactive reactivity with the parent, increasing the photohardening to an unsaturated group, and the occurrence of the crosslinking reaction is easily characterized as having an ethylenicity. Saturated base. It is a method of introducing a ethylatrophic group at the end of a polymer. ~ 'In the above-mentioned step of treating the polymer terminal isocyanate, the alcohol or the amine in the synthesis step of the polyurethane resin having an ethylenic bond in the side chain, only the ethyl group The unsaturated group is preferred because the control of the amount of introduction is such that the amount of introduction can be increased, and the efficiency of crosslinking reaction is increased. As the introduced ethylenically unsaturated bond group, it is not specifically prepared, and it is known that it is suitably selected according to the purpose, and the crosslinked cured film is formed into -34- "in accordance with the purpose, amines, etc.: in the final polyamine to be unsaturated The strength of the formate berylate is considered to be the same as that of the unsaturated residue. It is easy to use the same and the base. See, at other points s 201224663 'preferably methacryl fluorenyl, The propylene-based base, the stupid-ethyl base, and the methyl propyl (tetra)-based and propyl (tetra)-based groups are coexisting in the storage of the formable fresh material of the cross-linked cured film, and are particularly preferably a methacrylic fluorenyl group. There is no particular limitation on the amount of propylene in the base. It can be selected according to the purpose of the product. The ethyl ether unsaturated base equivalent is preferably 〇.〇5mmol/g~3.0mmol/g, more preferably 〇5赖〇1/ § ~ 2 "Heart, especially good for 0.75mm 〇 1 / g ~ 2.4mm 〇 1 / g, especially good for i 2 〇 〇 1 仏 ~ 2 * mmol / g. As a method for the V-unsaturated group in the main chain, there is a polyurethane vinegar

In the synthesis of the resin, a method of using a diol compound having an unsaturated group in the main chain direction is used for the Φ table, and the diol compound having an unsaturated group in the main chain direction is further described. The specific limitation can be appropriately selected according to the purpose, and the cis-type 2-butadiene decadiol, trans-_2_butylene diol, polybutadiene diol, and the like can be obtained. The polyamine phthalate resin having an ethylenically unsaturated bond in the side chain may also be used in combination with an alkali-soluble high score of a virgin methyl methacrylate resin having a different k from the specific polyamine phthalate resin. . For example, the polyurethane resin having an ethylenically unsaturated bond in the side chain may be used in combination with a polyamine phthalate resin having an aromatic group in a main chain and/or a side chain. Specific examples of the polyamine phthalate ester having an ethylenically unsaturated bond (1) are shown in, for example, Fukuokaro 0293" to "0310" of JP-A No. 2〇〇5 25〇43 8 The polymer of ρ-1 to p_31. Among these, the polymers of P-27 and P-28 shown in the paragraphs "0308" and "0309" are preferred.

S -35- 201224663 --(u) Polyamine phthalate resin obtained by reacting a carboxyl group-containing polyurethane with a compound having an epoxy group and an ethylenically unsaturated group in the molecule - A urethane resin is a polyamine phthalate resin (ϋ), which is a thiol-containing polyurethane having an isocyanide I® oxime and a diol containing a tickic acid group as an essential component. A polyamine phthalate resin obtained by reacting a compound having an epoxy group and an ethylenically unsaturated group. A low molecular weight diol having a mass average molecular weight of 300 or less or a low molecular weight diol having a mass average molecular weight of 500 or more may be added as a copolymer component as the diol component. By using the polyamine phthalate resin (ii), it is excellent in stability dispersibility or crack resistance or impact resistance with an inorganic filler, and heat resistance, moist heat resistance, adhesion, mechanical properties, and electrical properties are increased. high. Further, the polyurethane resin (ii) has a divalent isocyanate of a divalent aliphatic or aromatic hydrocarbon which may have a substituent, and a carbon atom and a nitrogen atom, and has a c00H group and two 0H. The carboxylic acid-containing diol as a reactant of the essential component, or the obtained reactant, and the pass-COO-bond, having an epoxy group and an ethylenically unsaturated group in the molecule (preferably described) The compound of the group represented by the formulae (1) to (3) is reacted. Further, the ♦ urethane resin (ii) is a diisocyanate kSa ' represented by the following formula (I) and is contained by the following formula (ΙΙ-1) to (ΙΙ-3). At least one selected from the acid-based monools is required to be A, and a polymer having a mass average molecular weight of from 800 to 3,000, represented by the following formula (IIM) to (ΙΠ_5), according to the purpose At least one of the reactants selected from the diol may also be a reactant obtained by the following formula (IV-1) to (ιν) having an epoxy group and an ethylenically unsaturated group in the molecule. The compound reacted.

S •36- 201224663 OCN—R^nqo General formula (I) H〇-R3-C-r4-〇h C〇〇H General formula (Π-1) H〇一R3-个卜R4_oh General formula (π - 2)

C〇〇H H〇~R3-N^r4~〇h General formula (π -3)

R1 in c〇OH, &quot;^ () represents a divalent aliphatic or aromatic cigarette which may have a substituent (e.g., preferably an alkyl group, an aralkyl group, an aryl group, an alkoxy group, or a halogen atom). Depending on the need, 'R' may also have any other functional group which does not react with an isocyanate group, such as an ester group, an amine phthalate group, a guanyl group, or a ureido group. In the general formula (II-1), 'R2 represents a hydrogen atom and may have a substituent [for example, a cyano group, a nitro group, a dentate atom (-F, -Cl, -Br, -I), -CONH2, _C〇〇). R0, -〇r6, -nhconhr6, -nhcoor6'-nhcor6'-oconhr6, _C0NHr6 (here, the ruler 6 represents an alkyl group having a carbon number and an aralkyl group having a carbon number of 7 to 15) An alkyl, aralkyl, aryl, alkoxy or aryloxy group. Among these, an aryl group having a hydrogen atom 'C 1 to 3 alkyl groups' and having 6 to 15 carbon atoms is preferred. In the formulae (Π-1) and (II-2), R3, R4 and Rs each may be the same or different and each represents a single bond and may have a substituent (e.g., an alkyl group, an 'aralkyl group is preferred).

a divalent aliphatic or aromatic hydrocarbon of S-37-.201224663, an aryl group, an alkoxy group, a halogen atom). Among these, 'the preferred one is an alkyl group having 20 carbon atoms, an alkyl group having 6 to 15 carbon atoms, and more preferably an alkyl group having 1 to 8 carbon atoms. Further, if necessary, other functional groups which do not react with an isocyanate group, such as a carbonyl group, an ester group, a carbamate group, a guanamine group, a urea group, or an ether group, may be contained in R3, R4 and R5. . Further, two or three of R2, R3, R4 and Rs may form a ring. Ar represents a trivalent aromatic hydrocarbon which may have a substituent, and an aromatic group having 6 to 15 carbon atoms. H〇-R7t〇-c-R8-c-R7-)-〇H Generalized” r\ r\ &quot;1 ΗΟ~^9~^·〇—c—R10-^—0H 〇η2 H〇- R9+〇—CO—R! Formula (Ban-3) Formula (Π-4) Formula (Π-5) In the formula (III-1)~(III-3), R7, R8 ' R9, Rl0 and Rll may each be the same or different. 'is a divalent aliphatic or aromatic hydrocarbon. The above r7, R! 0 and Rh are each preferably a C 2 to 20 alkyl group or a carbon number of 6 to 15 More preferably, the aryl group is preferably an alkyl group having 2 to 1 unit carbon atoms or an alkyl group having 6 to 10 carbon atoms. The above Rg represents an alkyl group having 1 to 2 carbon atoms. a carbon number of 6 to 15 aryl groups, more preferably a carbon number of 1 ~ 的 an alkyl group or a carbon number of ~ 10 aryl groups. Also, in the aforementioned r?, r8, R9, 丨〇 and Ri 1 ' may also be other functional groups that do not react with isocyanate groups, for example, HO-CH: 〒12 -CH-O--H n4 R^3 ho-(ch2ch=chch2)-( -ch2-ch-)^-oh -38- s 201224663 such as an ether group, a carbonyl group, a s-group, a cyano group, an alkene group, a carbamic acid aryl group, a decylamino group, a ureido group or a sulfonyl atom. In III-4), Rl2 represents a hydrogen atom, a stilbene group, an aryl group, Burning a cyano group or a halogen atom. Preferably, it is a hydrogen atom, a carbon number of 1 to 1 〇, a carboxyl group of 6 to 15 aryl groups, a carbon number of 7 to 15 aralkyl groups, : a radical or a functional atom, more preferably a hydrogen atom, a carbon number of ～6 groups, and a number of 6 to 1 aryl groups. a A ^ is also described in R! 2 It is a base which is reacted with an isophthalate group, and has a mercapto group in January, such as an alkyl group, a carbonyl group, an olefin fluorenyl group or a halogen atom, etc. In the formula (III-5), r main -# 彻, Rl3 is not square or cyano, more preferably A β 杳 &quot; ~ 10 aryl or cyano. More % is % 6 Γ 通式 (Πΐ-4), m means 2 ~4 number ^ (11 [-1) ~ (III-5), the number. The general formula number ' is preferably 2 to 100: I: 3, ... and ~ each represents 2 or more In the preferred formula (thoracic), ~ means 0 or 2 lives as 0 or 2~1〇〇. -39- 1 201224663

General formula 〇 7-1) Formula (IV-2) Formula 07-3) Formula (Han-4) Formula (W-5) &gt; Formula (W-6) Formula (W-7) y formula (汉-扪

P general formula 07-9) -40- 201224663

CHCHCHCH

General formula (IV-10&gt; Formula U v . Formula 07-12) Formula (W-13) Formula 07-14) Formula (ΒΓ-15) Formula (W-16) * I 丞 represents carbon The number 1 to 10 is an extended group, and R10 represents a hydrocarbon group having 1 to 10 carbon atoms. Show 0 or 1~1〇. Further, the polyamine phthalate resin (ii) can further reduce the low molecular weight of the acid group as the fifth component, and the formula (III-1) to (III-5) ^ Not the mass average molecular weight A. The low molecular weight diol 41-201224663 has a sufficiently low range of diols as long as the alkali solubility does not decrease in M2a and (10) does not decrease and the elastic copolymerization of the cured film is ensured. The low molecular weight which does not contain a carboxylic acid group can be added as a polycarbamic acid, and p eucalyptus (11) is particularly suitable for the diisononate of the formula (1). , at least one of the carboxylic acid group-containing diams represented by the formula (1)-1) to (Π-3), and the main component of the carboxylic acid group, according to the purpose, by the formula (III 1) (ΙΠ- 5) at least one selected from the group consisting of the polymer diol compounds having a mass average molecular weight in the range of the range of the formula or the formula (ΙΙΙ-1) to (ΙΙΙ-5) having a mass average molecular weight of 5 〇〇 The following reactant of the low molecular weight diol having no carboxylic acid group, and having any of the epoxy groups in the molecule and at least one of the formulae (IV-1) to (IV-16) An alkali-soluble photocrosslinkable polyamine phthalate resin obtained by reacting one (fluorenyl) acrylate-based compound with an acid value of 2 〇mgKOH/g~i; 20 mgK〇H/g. These polymer diol compounds may be used singly or in combination of two or more. Further, the above-mentioned polymer diol compound accounts for a solid content of the above-mentioned polyamine phthalate resin containing an acid group and an ethylenically unsaturated group, and is preferably 2% by mass to 3% by mass, more preferably 5% by mass. %~25 mass%. When the content is less than 2% by mass, the sufficient low modulus of elasticity at the time of high temperature of the cured film is not obtained, and if it exceeds 30% by mass, deterioration of developability or deterioration of the cured film is caused. - a method for synthesizing a polyurethane-containing polyamine phthalate with a compound having an epoxy group and an ethylenically unsaturated group in a molecule - as a polyurethane resin (ii) In the synthesis method, the above-mentioned diisocyanate compound and diol compound are heated in a non-protic solvent by adding a known catalyst corresponding to the activity of each reactivity.

S -42- 201224663 and synthesized. The molar ratio of the diisocyanate and the diol compound to be used is 0.8.1 to 1.2.1, and when the dispersing acid g is present at the end of the polymer, it is treated with an alcohol or an amine to finally form isocyanuric acid. The form of the base is synthesized. - Diisocyanate - The diisocyanate compound represented by the above-mentioned general formula (I) is particularly limited by the purpose, and may be appropriately selected according to the purpose, and examples thereof include the compounds described in the paragraph "〇〇21" of 2007-2030. The two molecular weight diols are not particularly limited as the high molecular weight compound represented by the above formula (III-1) to (III-5), and may be appropriately selected according to the purpose, for example, the special opening No. 2007-2030 The compound described in the paragraph "〇〇22"~" in the bulletin. The carboxylic acid group-containing diol __ is not particularly limited as the carboxylic alcohol compound represented by the above formula (II-1) to (11_3), and may be appropriately selected according to the purpose, for example, JP-A-2007-030, the compound of the "0047", etc. - a low molecular weight diol which does not contain a carboxylic acid group __ as a low molecular weight diol which does not contain a carboxylic acid group, and the other limitation 'may be For example, the amount of the copolymer of the compound described in the paragraph "(10)48" of the publication No. 2007-^30, and the diol having no carboxylic acid group, is preferably 95 mol% or less of the amount of the diol: More preferably, it is below 8〇%, especially below. When the amount of the copolymerization exceeds 95 mol%, an amine phthalate resin which is not excellent in properties can be obtained. When the ear is compared, there is no residue and no special opening. The diol is selected, and the example "0046 based on the choice of two" is not specifically opened. Low molecular weight 50% to imaging

S-43-201224663 Specific examples of the polyurethane resin (ii) obtained by reacting (ii) a carboxyl group-containing polyamine phthalate with a compound having an epoxy group and an ethylenically unsaturated group in the molecule For example, the polymers of ui to U4 and U6 to U1 1 shown in paragraphs "0314" to "〇315" of JP-A-2007-2030 can be cited as containing epoxy groups and ethylenic unsaturation. The epoxy acrylate of the base compound is replaced by glycidyl methacrylate, 3,4-% oxygen% hexyl methacrylate (trade name: Cyclomer A400 (manufactured by DAICEL Chemical)), 3, 4 -Epoxycyclohexyldecyl methacrylate (trade name: Cyclomer M400 (manufactured by DAICEL Chemical Co., Ltd.)), etc. - Polymer group-containing and ethylenically unsaturated group 3 S-group and ethylenically unsaturated group The content of the solid content of the amine phthalate resin (represented by the aforementioned polycarbamic acid-resin (1), (ii)) in the photosensitive composition is not particularly limited, and may be appropriately selected according to the purpose. Good for 5 mass% ~ 8 〇曰. / 14 „里/° 'More preferably 20% by mass to 75 篁/〇, especially preferably 30% by mass to 70% by mass. If the solid content is less than 5 mass od 0 / crack resistance, if it exceeds 8 If the mass is less than 5%, the solid content will not be maintained. If the content of the solid component is It is advantageous in the case of a good-acid group and an ethylenic unsaturated group. The average molecular weight... The mass of the amine phthalate resin is a flat acid group and an ethylenic unsaturated polyamine phthalate resin. And (聚), the polyamine phthalate resin. (There is no particular limitation in the prior art, which can be represented by two), and the mass average molecular weight is appropriately selected from the following, preferably

S '44. 201224663 2'〇〇〇~60,000, more preferably 2 000~50 000, especially good for 2 〇〇〇~〇(eight), especially good for 3,000~30,000, best for 5,000~30, 〇〇〇 . If the mass average is less than 2, if 子, a sufficient low modulus of elasticity will not be obtained at the high temperature of the cured film. If it exceeds 6 〇, 涂布, the suitability and development will be applied. Getting worse. In particular, the photosensitive composition of the present invention is excellent in dispersibility with an inorganic filler and excellent in crack resistance and heat resistance, and the non-image portion due to an alkaline developing solution is used. Excellent imaging. Further, the mass average molecular weight can be, for example, a high-speed GPC apparatus (East: HLC-802A manufactured by Soda Co., Ltd.) of 0.5 mass. / 〇 THF solution for the sample solution 'pipe column system using 1 ^ 61 HZM-M, injected 2 〇〇 from the sample, eluted with the aforementioned THF solution, at 25 it by refractive index detector or uv The detector (detection wavelength 254 nm) was measured. Next, the mass average molecular weight was determined from the molecular weight distribution curve corrected by standard polystyrene. - an acid value of an acid group-containing and ethylenically unsaturated group-containing polyurethane resin - an acid group-containing and ethylenically unsaturated group-containing polyurethane resin (the aforementioned polyamine phthalate resin (i) The acid value (solid content acid value) of (ii) is not particularly limited and may be appropriately selected according to the purpose, and is preferably 20 mgKOH/g to 120 mgKOH/g' more preferably 30 mgKOH/g to ll. The mg K〇H/g ' is particularly preferably from 35 mgKOH/g to 100 mgKOH/g. When the acid value is less than 2 〇 mgKOH/g ′, the development property is sufficient. When the acid value is more than 120 mg KOH/g ′, the development of the image is too high and the development of the image becomes difficult. Further, the acid value can be measured, for example, in accordance with JIS K0070. However, when the sample is not dissolved, use dioxane or tetrahydrofuran as a solvent. - Polyamine phthalate resin containing an acid group and an ethylenically unsaturated group 孓 ethylenically unsaturated group equivalent -- 5 -45- 201224663 Polyamine phthalate resin containing an acid group and an ethylenically unsaturated group The ethylenically unsaturated group equivalent of the polycarboic acid-based resin (i) and (ii) is not particularly limited and may be appropriately selected according to the purpose, and is preferably 0.05 mmol/g to 3.0 mm〇1/ g, more preferably 〇 5 〇 〇 1 ~ ~ 2 7 Yan 〇 1 々 'youjia is 0.75mmol / g ~ 2_4mmol / g, especially good! 2〇mm〇1/g~2 4 mmol/g. When the ethylenically unsaturated group equivalent is less than 〇 5 inm 〇 i / g, the heat resistance of the hardened film is deteriorated, and when it exceeds 3.0 mm 〇 1 / g, the crack resistance is deteriorated. The ethylenically unsaturated group equivalent can be determined, for example, by measuring the bromine number. The bromine number can be measured, for example, in accordance with JIS K2605. Further, 'the ethylenically unsaturated equivalent here is representatively a vinyl equivalent' which is the number of grams (Βι*2) of the resin to be measured for the 丨〇〇g obtained from the above bromine number (gB^ /ioog) is converted to the value of the molar number of additional bromine (ΒΓ2) per lg of resin. - Epoxy Resin Containing Acid Group and Ethylene Unsaturated Group _ Epoxy Resin Containing Acid Group and Ethylene Unsaturated Group The chemical structure can be used to form a polymer bond (1) (2) A series of acid and varnish types. (1) The series of polyethers and (2) the series of novolac type are represented as follows. First synthetic method: (a) an epoxy compound having at least two epoxy groups in one molecule, (b) a compound having at least two hydroxyl groups and one carboxyl group in one molecule, and (c) an ethylenically unsaturated group The reactant (I) of the monocarboxylic acid compound is further reacted with (d) a polybasic acid anhydride. Examples of the resin to be synthesized include those described in Japanese Patent No. 2877659.

S-46-201224663 Second Synthesis Method: The reaction product (π) of (a) one epoxy compound having at least two epoxy groups and (c) an ethylenically unsaturated group-containing monocarboxylic acid is further Polybasic anhydride reaction. The resin to be synthesized is, for example, a resin described in the Japanese Patent Publication No. 04/034 1 47, the Japanese Patent Publication No. 04-034. - Polyamide or Polyimine Resin - The polyamine or the polyimide resin is not particularly limited and may be appropriately selected according to the purpose, and for example, it is disclosed in JP-A No. 2,694. Recorder, etc. &lt;Polymerizable compound&gt; The above-mentioned polymerizable compound is not particularly limited, and may be appropriately selected for the purpose of having at least one radical polymerizable group in the molecule (Comparative) A compound which is preferably an ethylenically unsaturated group, preferably a monomer is more preferably a compound having a boiling point of 1 Torr at a normal pressure (for example, exemplified by a single group having a (fluorenyl) acrylate group A monomer selected from the group, at least 乍 is a monomer having a (meth)acrylic group, and no: limitation ' can be appropriately selected according to the purpose, and for example, it can be mentioned as an early (methyl) adienoic acid g Polypropylene glycol mono(meth)acrylic acid, monofunctional acrylate or monofunctional, such as acryl phenoxyethyl ester, glycerol, polyethylene glycol bis(indenyl) glycerol, Poly-didiol bis (in-methane acrylate, trimethylolethane triacrylate, trimethylol two-soil one) acrylate, trimethylolpropane diacrylate, neopentyl glycol two fields ~ one '^基

S -47- 201224663 )Acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tris(decyl)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(indenyl) acrylate, hexane two Alcohol di(meth)acrylate, trishydroxypropylpropane tris(propylene methoxypropyl)ether, tris(propylene decyloxyethyl)isocyanate, tris(propylene decyloxyethyl) Cyanuric acid ester, glycerol tri(meth) acrylate, tricyclodecane dimethanol (meth) acrylate, ethylene oxide or propylene oxide to trimethylolpropane or glycerin, bisphenol, etc. The polyfunctional alcohol addition reaction is carried out in each of the publications such as the publication of the publication of the Japanese Patent Publication No. Hei. No. Sho. The urethane acrylates described in each of the publications of the Japanese Patent Publication No. Sho-48-641, No. Sho. Epoxy acrylate such as reaction product with (meth)acrylic acid Polyfunctional acrylate or methacrylate and the like. Among these, more preferred are trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate. . The content of the solid content of the polymerizable compound in the photosensitive composition is not particularly limited, and may be appropriately selected according to the purpose, more preferably 2% by mass to 50% by mass, even more preferably 3% by mass to 40% by mass. Preferably, it is 4% by mass to 35% by mass. When the solid content is less than 2% by mass, the pattern cannot be formed, and if it exceeds 50% by mass, the crack resistance is deteriorated. On the other hand, when the content of the solid content is within the above-mentioned particularly preferable range, it is advantageous from the viewpoint of allowing good pattern formation and crack resistance to coexist. 〃

S 201224663 &lt;Photopolymerization initiator&gt; As a photopolymerization initiator, the ability to polymerize only is not particularly selected, for example, a bismuth oxadiazole skeleton, a phosphine oxide, an organic peroxide, and the like. A thio compound, a ketoxime ether or the like. In order to have a limitation capable of inducing a polymerizable compound, a living organism can be suitably used according to the purpose (for example, a three-hearing skeleton, a hexaarylbiimidazole, an anthracene derivative, a ketone compound, an aromatic rust salt, and the above-mentioned triterpene skeleton). The halogenated hydrocarbon compound is not particularly limited and may be appropriately selected according to the purpose, and examples thereof include a compound described in Bull. Chem. Soc. Japan, 42' 2924 (1969), and a British patent No. 1 388492. The compound described in the specification, the compound described in JP-A-53-133364, German Patent

5 of the compounds contained in the specification of 3337024 'F·C. Schaefer et al.

A compound described in Japanese Unexamined Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 6-2 - No. And a compound or the like described in the above-mentioned Japanese Patent No. 4,212,976, which is a compound of the above-described oxime-containing hydrocarbon compound, and the like. The material is not particularly limited, and may be appropriately selected according to the purpose. For example, the compound described in the paragraph "0085" of JP-A-2007-2030 may be mentioned. The ketone compound is not particularly limited, and may be appropriately selected according to the purpose, and examples thereof include a compound described in the paragraph "0087" of JP-A No. 20-7-3030.

In addition, the photopolymerization initiator other than the above is not particularly limited, and may be appropriately selected according to the purpose, and examples thereof include those described in the paragraph "〇〇86" of JP-A-2007-2030. Compounds, etc. Further, in order to adjust the exposure sensitivity or the photosensitive wavelength of the exposure to the photosensitive layer to be described later, a sensitizer may be added in addition to the photopolymerization initiator. The sensitizer can be suitably selected in accordance with a visible light beam, an ultraviolet laser, a visible light laser or the like which is a light irradiation means to be described later. The sensitizer can be excited by the active energy ray, and can generate free radicals by using other substances (such as a radical generator, an acid generator, etc.) for 9 (for example, energy movement, electron movement, etc.). The sensitizer which is useful as an acid or the like is not particularly limited, and can be appropriately selected according to the purpose. For example, a compound described in the paragraph "〇_" of JP-A No. 2, No. 3, No. 3, pp. As a photopolymerization initiator and a sensitizer „ , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , Electron-moving type-inducing initiator and sensitized coloring agent, (', [() electronic pigment (3) electron donating initiator, 増 residual color + and + hair agent (ternary starting line) The combination of the solid content of the sensitizer and the purpose of the sensitizer is also limited, and can be selected according to the week, and it is inclined to say, preferably 0 0... Ingredients and pregnancy are good for 0 · 0 5 〇 〇 / 〇 ~ 3 〇 | | 0 詈〇 詈〇 /, 胜 Λ Λ 〇 〇 〇 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 〇·2 mass〇/〇~10 mass 0/ negative solid content

When S-50-201224663 is 0.05% by mass, the productive agent will be photopolymerized from the photosensitive layer as photopolymerization, and may correspond to the above (X-aminoalkyl compound and hexadecyl double light as described below). The polymerization is not particularly high in mass% to 20,000 mass% by mass. The tendency to dissolve in the solid solid component is as follows: 'solid formation into a good pattern&lt;thermal crosslinking agent&gt; The oxygen of the epoxy-based calcined base of the above-mentioned base is less sensitive to the active energy ray, and the exposure procedure fee is lowered. If it exceeds 30% by mass, it is formed during storage. The phosphine-based ketones of the above-mentioned exposure light and the laser light having a wavelength of 405 nm, which are mentioned above, may be used in combination with one of the two types of initiators. The amine compound of the skeleton halogenated sensitizing agent is combined to form a composite 弁U imidazole compound or titanocene, etc. The solid content of the hair styling agent is limited by f, and can be appropriately selected according to the purpose, preferably. 〇% 'better than 0.5% by mass~1 When the content is less than 0.5% by mass, if the content is less than 0.5% by mass, if the exposed portion is more than 20% by mass, the heat resistance may be lowered. In the range of 1 ^ J % and good heat resistance, the binder is not particularly limited, and an epoxy resin or a polyfunctional oxygen heterocycle may be mentioned according to the purpose. In the calcination, it is preferred to have at least two cycloheximide compounds in one molecule and at least two oxocyclobutane compounds in one molecule.

S 201224663 : It is suitable for the above-mentioned epoxy tree wax to be selected, for example, 屮 pile door, ΛΛ, *''' a "0095 〇 〇 7-2030 bulletin paragraph 〇〇 9 public or In the paragraph of the official document No. 72340, "the compound contained in 〇1, etc. jr ^ is not particularly limited as the above-mentioned polyfunctional oxetane compound, and may be appropriately selected according to the purpose', 2007 2 Ω λ Π ^ ν ^ For example, the paragraph "Muller> Secret_", which is contained in JP-A-2007-2030唬, can be cited. ...the special restrictions on the photosensitive composition of the father's joints can be done according to the purpose:

The 〇 / / ^ ^ choice is preferably 1% by mass to 5C Berry. More preferably, it is 2% by mass to 4% by mass%. When the heart is 3 mass% to 30, the heat resistance is deteriorated, and the properties are deteriorated. On the other hand, a good cured film can also be used for heat resistance. When the solid content is less than 1 mass%/〇, and more than 50 mass%, the development property or crack resistance is obtained, and if the solid content is the above-mentioned excellent degree sensitivity, a cured film is formed, and crack resistance can be formed. It is advantageous from the viewpoint of coexistence &lt;&lt;Other thermal crosslinking agents&gt;&gt; Other thermal crosslinking agents may be added separately from the aforementioned cyclobutane compound. As a limitation of other menthosides or polyfunctional oxyheterocycles, the thermal crosslinking agent can be appropriately selected according to the purpose, and there is no paragraph "200798" of the 2007-2030 publication, for example, a special opening and closing can be cited. "Chemical elastomer" as described in "0100" is suitable as a thermoplastic elastomer, and may be suitably selected, for example, by a stupid y 叼 limitation, and may be an olefin-based elastomer or an olefin-based bomb. 201224663 Sex, alkaloids, s-based elastomers, polyester elastomers, polyamines, acrylic ruthenium and poly-xylylene elastomers The lanthanum is composed of a hard segment component and a soft segment component. Generally, it is a right-handed, strong-bodied heat-resistance and strength, and the latter contributes to a soft elastic system such as Special Opening 2〇〇7_1 99532 It is described in the "〜2〇7" of the bulletin. 197 " &lt;Heat-hardening accelerator&gt; As a thermosetting accelerator, it is not particularly limited, and it is preferable to select a pendulum. For example, "τ..., for example, paragraph 〇101 of JP-A-2007_2030 The compounds described in the above. The content of the solid content of the hardening accelerator in the photosensitive composition is not particularly limited, and may be appropriately selected according to the purpose, and is preferably 0.1 mass% (10) mass%, more preferably 0.05 mass. %〜15质量百分比,: preferably 0.1 mass. /〇~丨〇质量%. If the solid content is less than the G.Qlf amount, the hardening power H cannot be exhibited. If the content is higher than (4), the photosensitive composition is On the other hand, if the content of the solid content is within the above-mentioned particularly preferable range, it is advantageous from the viewpoint of coexisting the storage stability of the photosensitive composition and the good physical properties of the cured film. &lt;Colorant&gt; The colorant is not particularly limited and may be appropriately selected according to the purpose, and a dye selected from a coloring pigment or a well-known dye may be used.

S -53- 201224663 Appropriate i| 0106 j &lt;Intimately suitable for 0108" The density of the 0.1-size solid film will not change, and the film will be treated as follows: "0113 &lt;Other j" is suitable for the selection of 醯, 醯 amine: 1 series, etc. i: colored color # ' is not particularly limited, and may be selected according to the purpose - for example, the special publication 2007.2030 In the paragraph "The compound described in the above. The accelerator" is not a special (4), and may be selected according to the purpose. For example, the compound described in the paragraph "2007-0730" may be mentioned. The solid content of the accelerator in the photosensitive composition, and the other: the product can be appropriately selected according to the purpose, preferably 0.01-20% by mass, more preferably 0.1% by mass to 15% by mass, Particularly preferred is %~10 mass. /〇. If the content of the body component is lower than o.WM, the hardening early edge property will not be exhibited. If it exceeds 2 〇 mass%, the photosensitive composition is preserved and the surface is solid. If the content is the above-mentioned excellent one, the preservation stability and the goodness of the photosensitive composition can be improved. It is advantageous from the point of view of coexistence. Inhibitors &gt; Island thermal polymerization inhibitors, You, Lux, ^, J, and there are special restrictions, according to the choice of 'for example, can be cited A compound or the like described in paragraph 2 of the Japanese Patent Publication No. 7-2030. In addition, the other ingredients of the island 'do not win m, m special limited emperor can be learned according to the purpose, for example, can be used such as Bent〇n, montmorillonite, gas ^: Additives for the agent, polyoxygenated system, fluorine-based, high-score 'smoothing agent and leveling agent. Sub-54- 1 201224663 &lt;Organic solvent&gt; The organic solvent is not particularly limited, and may be appropriately selected according to the purpose, and for example, the paragraph of "Japanese Laid-Open Patent Publication No. Hei 1-240930" 〇 or special compound of p ^ r · + 〇 43" ant Luo "0121" of 2007-2030. The content of the photosensitive composition is not limited, and may be appropriately selected according to the purpose of the invention, preferably i mass% to 8 〇, preferably 2 mass. /. ~70% by mass, especially good for 3 mass% ~ 6〇 quality. :. If the content of the composition is less than 1% by mass, the viscosity of the composition is high, and the formation of the abdomen becomes difficult. When the film is more than 80% by mass, the desired film thickness becomes difficult. In the case where the content of the other two is within the above-mentioned range, it is advantageous from the viewpoint of the suitability of the coating film 1 and the clothing k. The photosensitive composition (photosensitive film) can be used as a liquid photoresist by coating and drying on a substrate having a conductor wiring = a substrate, and is particularly suitable for the production of a photosensitive film. The photosensitive film is not limited to the first embodiment, and has at least the support i and the sensation 3, and preferably has the protective film 3, and may have a buffer layer if necessary: oxygen barrier A layer (hereinafter referred to as a % layer) or the like is formed. The shape of the photosensitive film can be you, VJ dying &amp;, inch, J ❿ heart, you / have special. Restrictions, can be selected according to the purpose, for example, in Li Yi Niu Yin Shi and marry in order In the form of a photosensitive layer or a protective film, the PC layer, the photosensitive layer, and the protective film are sequentially formed on the yoke support, and the buffer layer is sequentially provided on the support. The PC layer, the light-forming layer, and the form in which only the mouth e 3 is in a thin layer. Furthermore, the photosensitive layer may be a single layer or a plurality of layers. The photosensitive layer is formed of a photosensitive composition.

S-55-201224663 The photosensitive enthalpy is not particularly limited, and the photosensitive agent and the object of the present invention are appropriately selected as long as they contain an inorganic filler, and examples thereof include a composition and the like. The total content of the photosensitive composition is 3% by mass or more. 3 〇% by mass to 75% by mass of the inorganic filler in the solid content, Π〇% by mass to 8% by mass, more preferably 35% by mass to 8 Å by mass; 2 narration, preferably 35 mass% or more (more preferably 40 mass% or more ^ 'more preferably 35 mass 4 % to 75 mass%) 40 mass % to 75 mass 乂 preferably 40 mass % to 80 mass %, more preferably % 〜 80 % by mass, better. 'Uganjia is 50 quality. / 〇 (preferably 50 mass 贞 · $ 〇 / 75 皙鼍 In the present invention, sensitization is negative/〇). • s above. If the melting viscosity is lower than lxl〇 C, it is particularly preferably lxl〇5pa, and the photosensitive layer is 70. : Two edges melted and deteriorated. The average particle size is less than 〇_3μηι^ field inorganic filler, and the flatness is 5 X 1 0 3 p a · q U ^ 2xl 〇 3Pa.s or less. If it is more than a 8 or less, the best one is 5xio3pa.s. On the other hand, when the inorganic ruthenium is right like AA, it will be poorly laminated. · The average grain handle of the filling agent &» &quot;2 . , especially good for 2xl 〇 3Pa.SJ ^ 上上上仏 仏. 3μιη以上下下的中的1 5χΐη3Ρ 、, -it preferably 1.0 Xl03pa.sj^ 下巧·5 10 Pa.S Below, it is worse. under. If it exceeds 2Xl〇3Pa.s, the embedding property will be sufficient if the melt viscosity of the photosensitive layer at 70 °C is better, and the laminate is poorly covered and buried. In the case of the measurement of the viscous viscosity of the photosensitive layer, it is possible to use a rheology leaf VAR-1000 (10) EOLOGICAL Co., Ltd.) or a daisy coffee DD-m type (made by Toyo BALDWM Co., Ltd.). It is measured by a melt viscosity measuring device. The details of 201224663 are as described in the paragraph "0127". Further, the coating liquid prepared from the photosensitive composition or the coating liquid to which the organic solvent is added in the composition has a viscosity of 50 cp or less, more preferably 30 cp or less. The viscosity of the coating liquid was measured by, for example, τ 〇 KI to make white f VISCOMETER RE-80. The photosensitive film of the present invention is preferably a coating liquid which can be formed by the above or a coating containing a photosensitive composition (permanent pattern and permanent pattern forming method). The permanent pattern of the present invention is obtained by the permanent method of the present invention. . The permanent pattern is as described in the paragraph "0283" of JP-A-2007-2030. (Printed substrate) The printed substrate of the present invention has a permanent pattern formed by a method of forming a substrate on a substrate. Furthermore, other configurations are required. The other structure is not particularly limited, and may be appropriately selected, and examples thereof include a build-up substrate on the edge layer between the substrate and the permanent pattern. [Examples] Examples of the invention are described below, but are defined by the examples of the present invention. The binder resins i to 7 are synthesized as follows (synthesis example -57- "01 15" to a segment or at a sensitivity of 25 ° C, preferably i-form can be produced by E 〖product name. photosensitive composition liquid. Forming side: Falling "0128" The above permanent drawing should also have the same purpose according to the purpose. 7) 〇S. 201224663 (Synthesis Example 1) The composition of the binder resin 1 is added to the mass of 2,20 加入. Parts (equivalent equivalent) of cresol/novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., E〇CN_1〇4S, softening point 92t, epoxy when straight 220), 134 parts by mass (1 m) Propylene glycol monodecyl ether, 648.5 parts by mass (9 moles) of acrylic acid, 46 parts by mass of methylhydroquinone, hydrazine 131 parts by mass of carbitol alcohol acetate, and 484 parts by mass of solvent oil, heated At 90 ° C, stir to dissolve the reaction mixture. Next, the reaction liquid was cooled to 6 Torr (:, 13.8 parts by mass of triphenylphosphine was added, and heated to 1 Torr. 0, and the reaction was carried out for about 32 hours) to obtain an acid value of 〇5111§1&lt;:〇11/ § The reactant (hydroxyl group, 12 equivalents). Next, 3647 parts by mass (24 moles) of tetrahydrophthalic anhydride, 13.7 parts by mass of carbitol acetate, and 58.8 parts by mass of a solvent were added thereto. The oil was heated to 95 ° C, and the reaction was carried out for about 6 hours to carry out cooling. The acid value of the solid component was 4 〇 mg KOH / g, and the concentration of the solid component was diluted to 4% by weight. Unsaturated polycarboxylic acid resin (adhesive resin 丨). (Synthesis Example 2) Synthesis of binder resin 2 475 parts by mass of YDF2 〇〇1 (made by Tohto Kasei Co., Ltd., bisphenol F type epoxy) Resin), 72 parts by mass of acrylic acid, hydrazine. 5 parts by mass of hydrogen, 1 20 parts by mass of carbitol acetate, heated to 90, stirred to dissolve the reaction mixture. Secondly 'cooled to 60 it, added 2 parts by mass of benzylated trimethylammonium chloride, heated to 1 〇〇. (:, reaction until the acid value becomes 1 mgK Then, 98 parts by mass of maleic anhydride and 85 parts by mass of carbitol acetate' were heated to 8 (TC, reacted for about 6 hours) for cooling, and diluted with carbitol acetate. The solid content concentration was made 4% by mass to obtain an acid-modified epoxy resin containing an ethylenically unsaturated group.

S:58-201224663 (Synthesis Example 3) Synthesis of the binder resin 3: 350 parts by mass of the component EXA-7376 (manufactured by Dainippon Ink and Chemicals Co., Ltd.), 70 parts by mass of the A2 component acrylic acid, and 0.5 part by mass of A The hydroquinone, 120 parts by mass of carbitol acetate' was heated to 90 ° C, stirred to allow the reaction to completely dissolve the mixture. Next, the obtained solution was cooled to 60 ° C, and 2 parts by mass of triphenylphosphine was added and heated to 100 T: until the acid value of the solution became 1 mgKOH/g. 9 parts by mass of the maleic anhydride of the A4 component and 85 parts by mass of the carbitol acetate were added to the solution after the reaction, and the mixture was heated to 80 ° C for about 6 hours, and then cooled to form a card. The alcohol-containing acetate was diluted so that the solid content concentration became 40% by mass to obtain a solution of the component A. The component A is a reaction product obtained by reacting (A1) a epoxidized propyl ether of a bisphenol formaldehyde resin with (A2) an unsaturated sulfhydryl compound having a ethylenically unsaturated group and a thiol group (hereinafter referred to as " A3 component ")" A resin having an ethylenically unsaturated group and a slow group formed by reacting with (A4) an acid anhydride. (Synthesis Example 4) Synthesis of the binder resin 4: 400 parts by mass of the A1 component YDPF-l (manufactured by Tohto Kasei Co., Ltd.), 72 parts by mass of the A2 component acrylic acid, and ruthenium 5 parts by mass of the fluorenyl nitrogen醌, 120 parts by mass of carbitol acetate is added to the reaction vessel and heated to

The reaction was allowed to proceed by stirring at 90 ° C, and the mixture was allowed to react while being completely dissolved. Next, 'cool the obtained solution to 6 (TC, add 2 parts by mass of the three stupid scales, heat to loo c, and react to make the acid value of the solution become. Add 1 part by mass to the solution after the reaction. The tetradecyl phthalate needle of the eighth component and 85 parts by mass of carbitol acetate were heated to 8 Torr (&gt;c A for about 6 hours, cooled, and diluted with carbitol acetate vinegar A solution of the component A was obtained by setting the solid content concentration to 40% by mass.

S-59-201224663 The above-mentioned A component is a reaction product obtained by reacting (A1) a propylene glycol ether of a bisphenolfurfural resin with (A2) an unsaturated carboxyl compound having an ethylenically unsaturated group and a carboxyl group (hereinafter) A resin having an ethylenically unsaturated group and a carboxyl group formed by reacting with the (A4) acid anhydride is referred to as "A3 component". (Synthesis Example 5) The synthesis of the binder resin 5 was carried out in a flask equipped with a stirrer and a reflux condenser, and 四0 g (solid content: 60% by mass of 〇.〇1 mol) of a four-acid-low-acid needle having a guanamine bond was added ( Ml), 2.87 g (0.007 mol) 4,4'-[isopropylidene bis(p-phenoxy)diamine (BAPP), 1.36 g (0.003 mol) Jeffamine D400 (Sankai Chemical Precision) 2, 2.82 g of dimercaptoacetamide was stirred at room temperature for 8 hours to obtain a polyamidene precursor (p2) having a guanamine bond of the component (A). The obtained polyimide intermediate had a repeating structure shown below, and had a mass average molecular weight of 30,000' solid concentration of 4% by mass. (Synthesis Example 6) Synthesis of the binder resin 6 in a 50 〇mL three-neck round bottom flask equipped with a condenser and a stirrer '32.00 g (0.216 mol) of 2,2-bis(hydroxymethyl)propionic acid (DMPA) And 9.00 g (0.009 mol) of polypropylene glycol (molecular weight 1 Torr) (ppG1 〇〇〇) was dissolved in 118 mL of propylene glycol monomethyl ether monoacetate. 37.5 4§ (0.15 mol) 4,4-diphenylmethane diisocyanate (1), 0.1 § 2,6--second butyl hydroxy benzene, 〇28\6〇^3111 ;-60 0 (made by Nitto Chemical Co., Ltd.), after stirring at 75 ° C for 5 hours, 9 · 6 ! g methanol was added. Then, 17.91 g (〇.126) was added as a epoxide containing an ethylenically unsaturated group, and a glycidyl acrylate (GMA) and a catalyst of 5,000 ppm were added.

-60-S 201224663 Triphenylphosphine was stirred at 1 1 ° C for 5 hours and then cooled to room temperature to obtain 2 14 g of a polymer solution. The above-obtained binder resin 6 (acid-modified ethylenically unsaturated group-containing polyamine phthalate resin) has a solid content concentration of 40% by mass and a solid content acid value of 75 mgKOH/g as a gel permeation layer. The mass average molecular weight (polystyrene standard) measured by the analysis (GPC) was 12, and the ethylenically unsaturated group equivalent was 1.3 mmol/g. (Synthesis Example 7) Synthesis of the binder resin 7 in a 500 mL three-neck round bottom flask equipped with a condenser and a stirrer '10.22 g (〇.〇69 mol) 2,2-bis(hydroxyindole)butyric acid ( DMBA), 12.97g (0_081 mol) glycerol monodecyl acrylate (〇[Μ) and 4.80g (0_004 mol) polypropylene glycol (molecular weight 12〇〇) (ppGl2〇〇) dissolved in 79mL of propylene glycol monodecyl In ether monoacetate. Add 37.54 § (0.15 mol) 4,4-diphenylmethane diisocyanate (River 1) 1), 〇.1 § 2,6-di-t-butyl hydroxy benzene, 〇.2g as a touch The trade name of the media: Neostan U-600 (made by Jidong Chemical Co., Ltd.), at 75T: heating and disturbing for 5 hours. Then, it was diluted with 9.61 mL of methanol, and stirred for 3 minutes to obtain 145 g of a polymer solution (solid content concentration judged by mass%). The obtained binder resin 7 has a solid content acid value of 65 mg K〇H/g, and a mass average molecular weight (polystyrene standard) determined by gel permeation chromatography (GPC) is 1 5,000 'ethylenic unsaturation. The basis weight was 1.26 mmol/g ° (Example 1 series) The surface-treated fillers 1 to 6 were synthesized as follows (Preparation Example 丨~^).

S-61 - 201224663 (Preparation Example 1) Preparation of surface-treated filler 1 For 100 parts by mass of vermiculite particles (trade name: s〇_c2, manufactured by ADMATECHS, average particle diameter (d5〇): 〇», add i A mass fraction of a decane coupling agent of the following structural formula (trade name: kbm_573, manufactured by Shin-Etsu Chemical Co., Ltd.) was subjected to a decane coupling treatment to prepare a surface-treated filler 1. /=\ och3 "~NH-CH2CH2CH2-Si- OCH3 OCH3 (Preparation Example 2) Preparation of surface-treated filler 2 For 182 parts by mass of filler (trade name: b _ 3 〇, manufactured by Suga Chemical Co., Ltd., average particle diameter (d50): 〇·3μηι, barium sulfate 1) 1 part by mass of Shishi Burning Coupling Agent (trade name: KB Μ-573, manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and a decane coupling treatment was carried out to prepare a surface-treated filler 2. (Preparation Example 3) Surface-treated filler 3 In the case of 100 parts by mass of vermiculite particles (trade name: SO-C2, manufactured by ADMATECHS, average particle diameter (d50) ··〇.5μη1), 1 part by mass of a decane coupling agent of the following structural formula is added (product Name: ΚΒΜ-403, Shin-Etsu Chemical Industry Co., Ltd.) Silicon coupling treatment for burn "to the surface treated filler modulation 3. och3

Ci^2~^CH-CH2-〇-CH2CH2CH2-Si-OCH3 〇OCH3 (Preparation Example 4) Preparation of surface-treated filler 4 For 100 parts by mass of vermiculite particles (trade name: SO-C2, manufactured by ADMATECHS, average Particle size (d50) : 〇.5μιη), add 1

S-62-201224663: KBM-903, 填料 偶 coupling treatment (trade name: Shin-Etsu Chemical Co., Ltd.) was prepared by modulating the surface mass portion of the following formula. ?ch3

NH2 OH2CH2CH2—Si—'〇CH 0〇Η3 (Preparation Example 5) Modification name of surface-treated filler 5: SO-C2, .5 μηι), Timing port 1 ^ : ΚΒΜ-1003, with modulation table for 10 0质量 偶 粒子 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( Treatment of filler 5. 〇ch3 I 6 CH2 di CH-CH2 Ningbu OCH3 och3 (Preparation Example 6) Surface treatment filler 6 Modification name: SO-C2, • 5 μ m ), adding force α 1 ;: HMDS-3,调制 粒子 粒子 ( 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 调制 ( ( ( ( ( ( ( ( ( ( ( ( ( ), the decane coupling treatment is carried out to treat the filler 6. CH3 ?H3 CH3 - Si - ΜΗ - S1 - CH3 CH3 ch3

S-63-201224663 (Example 1-1) &lt;Preparation of photosensitive composition coating liquid> The following components were mixed to prepare a photosensitive composition coating liquid. The viscosity of the photosensitive composition coating liquid was measured using an E-type viscometer (trade name: vjscOMETER RE-80, manufactured by TOKI). The binder resin synthesized in Synthesis Example 1 3 2.3 parts by mass of coloring pigment: HELIOGEN BLUE D7086 (manufactured by BASF Corporation) 0.021 parts by mass of coloring pigment: Pariotol Yellow D0960 (manufactured by BASF Corporation) 0.006 parts by mass of polymerizable compound: DCP-A ( Co., Ltd.) 5.3 parts by mass of initiator: Irgacure 907 (manufactured by B ASF) 0.6 parts by mass of sensitizer: DETX-S (manufactured by Sakamoto Chemical Co., Ltd.) 0.005 parts by mass of reaction auxiliary : EAB-F (Protected by Guji Chemical Co., Ltd.) 0.019 parts by mass of hardener: melamine (trade name: manufactured by Wako Pure Chemical Industries, Ltd.) 0.1 6 parts by mass of thermal crosslinking agent: Epototho YDF-1 70 (Dongdu Huacheng ( 2.9 parts by mass of inorganic filler: surface treatment filler 1 1 6 · 0 mass parts ion trapping agent: IXE-6107 (manufactured by Toagosei Co., Ltd.) 0.82 parts by mass of coating aid: Megafac F-780F 0.2 parts by mass (large Japan Ink (stock): 30% by mass of mercaptoethyl ketone solution) Elastomer: Espel 1612 (manufactured by Yuli Chemical Industry Co., Ltd.) 2.7 parts by mass

S -64 - 201224663 38.7 parts by mass of cyclohexanone (solvent) - Preparation of photosensitive film _ Using a polyethylene terephthalate film (pET) having a thickness of 25 μm as a support, on the support, The photosensitive composition coating liquid was applied by a bar coater so that the thickness of the dried photosensitive layer was about 30 μm, and dried in a hot air circulating dryer at 80 ° C for 3 minutes to prepare a photosensitive film. . For the photosensitive film, a rheometer VAR_1〇〇〇 type (manufactured by RHE0L0GICAL Co., Ltd.) was used, and the viscous viscosity of the sensory layer was measured under the following conditions. - Melt Viscosity Measurement Conditions - The melt viscoelasticity was measured at a strain of 0 005 and a frequency of 1 Hz using a plate having a diameter of 20 mm. Further, the temperature range was set to 25 to 85 χ: and the measurement was performed at a temperature increase rate of 51 /min. &lt;Formation of permanent pattern&gt; - Modulation of laminated body

Next, as a substrate, the surface of a copper clad laminate having a wiring and a through-hole of a printed wiring board having a copper thickness of 1 2 μm was prepared by applying a polishing treatment. On the copper-clad laminate, the photosensitive layer of the photosensitive film is contacted with the copper-clad laminate, and is made of N1 Chig0-M〇rt〇n (manufactured by N1 Chig0-M〇rt〇n). VP130) laminates a layered body in which the copper-clad laminate, the photosensitive layer, and the polyethylene terephthalate film (support) are laminated in this order. - A pressure-bonding condition is pressed at a temperature of 70 ° C, pressing pressure 〇 2 Μ ρ &amp; force, time ... 10 seconds. .

S-65-201224663 - Exposure Step - For the above-mentioned photosensitive layer in the laminated body, the self-polymerizing p-benzoquinone s- 乙 曰 film (support) side, using the exposure substrate EXM-immc of the circuit board The company made exposure by a mask to 4 〇mj/cm2 to harden the _ region of the photosensitive layer. - Imaging step - After standing at room temperature for 10 minutes, the polyethylene terephthalate film (support) is peeled off from the laminate, and the photosensitive layer on the copper-clad laminate is used in a total mass of 1 mass. The % sodium carbonate aqueous solution was used as an alkali imaging solution, and sprayed for development at a pressure of 30 (:, 〇.181^&amp; (1.81^£7 (:1112) for 6 sec seconds to dissolve and remove the unexposed area. Then, After washing with water, it was dried to form a permanent pattern. The obtained image was used to evaluate the developability and sensitivity. - Hardening treatment step - The entire laminate in which the permanent pattern was formed was heat-treated at 15 ° C for 1 hour. The surface of the permanent pattern is hardened to increase the strength of the film, and a test plate is produced. The measurement and evaluation of the reliability test are as follows. The viscosity of the coating liquid of the photosensitive composition includes the measurement result of the viscous viscosity of the photosensitive layer. The results of these measurements are shown in Table 1 below. &lt;Evaluation method&gt; - Evaluation of embedding - Observation of the photosensitive layer to L / S by using an optical microscope at a magnification of 50 times to 2 times ( Line/gap) = 5 0 μ m / 5 0 μ m between wiring patterns Embedding state, evaluated according to the following criteria.

-66- S 201224663 [Evaluation Criteria] 〇: The photosensitive film is embedded in the step of the pattern circuit and the base film, and no gap is formed between the photosensitive film and the copper-clad laminate of the circuit. Case △: a case where a gap occurs between the photosensitive film and the copper-clad laminate of the above-mentioned circuit, or a bubble of air or the like occurs between the pattern circuit and the photosensitive layered body Δ x : the melt viscosity is too low, Although the bubbles do not enter the substrate during lamination, the photosensitive layer oozes a large amount from the substrate and the support. X: The melt viscosity is too high to be laminated - Thermal shock resistance (crack resistance) (TCT) - as reliability In the test item, the appearance of cracking or peeling was evaluated by a temperature cycle test (TCT). The TCT system uses a gas phase hot and cold tester to place the electronic component modules in the gas phase at -5 5 ° C and 1 25 ° C for 30 minutes, as a cycle of 1,000 cycles and 1,500 cycles. The heat shock resistance was evaluated by the following criteria. [Evaluation Criteria] 〇: No crack occurred. △: There is a shallow crack. X: There is a deep crack. - Insulation (HAST) - The copper foil of a printed circuit board having a thickness of 12 μm thick copper foil laminated on a glass epoxy substrate was subjected to etching, and the line width/gap width was 50 μm / 50 μm, and the wires did not touch each other. , the comb-shaped electrodes on the same side facing each other are obtained. -67- 201224663 A solder resist layer was formed by a general method on the most electrode, and exposure was performed at two (40 mJ/cm2). Secondly, at room temperature, the fog shows t 赃 (four) amount% (four) steel water material for 20 seconds. The company uses the UV-irradiated clothing 衣 1 J / c m2 詈 pin salt well drawer; 隹 ~ , ...Λν In the illusion month b, the pentad nine layer is irradiated with ultraviolet rays. Further, the substrate for evaluation was heat-treated with i C for 6 minutes. "The comb-shaped electric power is applied to the laminated body for evaluation after the formation of the solder resist J: the solder wire of the polytetrafluoroethylene is connected to the same by the Sn/Pb solder." After the electrode, the laminated body for evaluation was placed in a 13 (rc, 85% RH super-acceleration high-temperature and high-humidity life test (HAST) tank in a state where a voltage of 5 〇v was applied to the laminated body for evaluation. 〇〇 。 。 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉 藉Excellent 。 △ • The migration was slightly observed on the copper, but the insulation was good. △: The migration was observed to be slightly inferior in insulation. X: Short circuit between electrodes, poor insulation. _ Solder heat resistance (resistant to heat Reflow-re-stuction) - Apply a rosin-based flux or a water-soluble flux to the test piece and immerse it in a 26 〇t solder bath for 1 sec. This is 1 cycle and repeats 6 cycles. The appearance of the coating film was visually observed and evaluated by the following criteria. [Evaluation Criteria] 〇: No appearance in the coating film Abnormal (peeling, bulging), no penetration of solder.

-68- S 201224663 △. The coating film is filled with abnormalities (peeling, bulging) or solder penetration but to a lesser extent. X: There are many abnormalities (peeling, bulging) in the appearance of the coating film, or there is penetration of the solder and the degree is heavy. - Evaluation of analytical property - The photosensitive laminate was allowed to stand at room temperature (23 ° C) and 55% RH for 10 minutes. From the polyethylene terephthalate film (support) of the obtained photosensitive laminate, the exposure machine EXM-U72 (manufactured by 〇RC Co., Ltd.) for the circuit board was used to pass the width of the diameter 5 〇μΓη 2 The mask of the round hole pattern of 〇〇μιη was exposed at 40 mJ/cm 2 . The exposure amount at this time is the light energy necessary for curing the photosensitive layer of the photosensitive film in the evaluation of the sensitivity. After standing at room temperature for 丨〇 minutes, a polyethylene terephthalate film (support) was peeled off from the photosensitive laminate. For the entire photosensitive layer on the copper-clad laminate, spray the above-mentioned 30% C 1% by mass sodium carbonate aqueous solution as a developing solution at a spray pressure of 1515 MPa for twice the shortest development time. To dissolve and remove the unhardened area. The surface of the copper-clad laminate having the cured resin pattern thus obtained was observed with an optical microscope. The smallest round hole pattern in which no residue was observed at the bottom of the circular hole of the pattern, and no abnormalities such as rolling up and peeling of the pattern portion were formed, and a gap was formed. The width, which is taken as the resolution, is evaluated by the following criteria. The smaller the resolution coefficient value, the better. [Evaluation Criteria] 〇: A circular hole having a diameter of 90 μm or less is analytically excellent.

S -69- 201224663 〇 △: A circular hole having a diameter of more than 90 μm and a thickness of 120 μm or less is analytically good. △: A circular hole having a diameter of more than 120 μm and a thickness of 200 μm or less can be analyzed, and the resolution is slightly inferior. X: The hole system cannot be resolved and the resolution is poor. (Examples 1-2 to 1-7) In the example 1-1, 'in addition to the binder resin 1 synthesized in Synthesis Example 1', the binder resin synthesized in Synthesis Examples 2 to 7 was used 丨_2~丨·7 As shown in the following Table 1, 'the photosensitive liquid composition coating liquid was prepared in the same manner as in Example 1_丨, and the viscosity of the coating liquid was measured, and the coating liquid was used and Example 1 _ 1 The photosensitive film was produced in the same manner, and reliability evaluation was performed in the same manner as in Example 1_丨. The results obtained are shown in Table 1 below. (Example 1-8) In Example 1-6, instead of the surface-treated filler 1 as an inorganic filler, the surface-treated filler 2 was used, and as shown in Table 2 below, sensitization was carried out in the same manner as in Example 1-6. The coating liquid of the composition was measured for the viscosity of the coating liquid, and a photosensitive film was produced in the same manner as in Example 1 to 6 except that the coating liquid was applied, and the reliability was evaluated in the same manner as in Example 1-6. The results obtained are shown in Table 2 below. (Examples 1-9 to 1-1 1) In the same manner as in Example 6-1, except that the photosensitive composition coating liquid was changed to the composition ratio not shown in Table 2 below. The viscosity of the coating liquid was measured, and a photosensitive film was produced in the same manner as in Example 1-6, and the reliability was evaluated in the same manner as in Example -6. The results obtained are shown in Table 2 below.

S. 70-201224663 (Comparative Examples 1 -1, 1 - 3, and 4) In Example 14, 4, SO-C2 (ADMATECHS Co., Ltd.) which was surface-treated without the use of the Shiki production agent was used as the inorganic filler. Even, clothing, stone (as shown in the following Table 3), prepared in the same manner as in Example 丨6, ^', the viscosity of the coating liquid was determined, and the coating liquid was used again, and the same image as the example 丨 6 The photosensitive film was produced in the same manner as in Example 1 and 6. The reliability was obtained. The results obtained are shown in Table 3 below. &lt;Comparative Example 1-2 In Comparative Example 1-1, the adhesive resin 1 synthesized in Synthesis Example 1 was used instead of the adhesive portion synthesized in Synthesis Example 6, as shown in Table 3 below. In the same manner as in Comparative Example 1-1, the photosensitive composition coating liquid was prepared, and τ and 'the viscosity of the coating liquid was determined. Then, the coating liquid was used, and a photosensitive film was produced in the same manner as in Comparative Example 1 and β. Comparative Example i_i performs reliability evaluation in the same manner. The results obtained are shown in Table 3. (Comparative Example 1 - 5 to 1 - 8) In Comparative Example 1-1, instead of the non-decane coupling agent, SO-C2 (manufactured by ADMATECHS Co., Ltd., 矽石j, using a preparation example) As shown in the following Table 3, as shown in the following Table 3, the photosensitive composition coating liquid was prepared in the same manner as in Comparative Example ,, and the viscosity of the coating liquid was measured, and the coating liquid was further used. A photosensitive film was produced in the same manner as in Comparative Example 1 _ .. The reliability was evaluated in the same manner as in Comparative Example 1-1. The results obtained in Table 3 below are shown.

S -71 - 201224663 [Table i] Ingredient Example 1-1 1-2 1-3 1-4 1-5 1-6 1-7 Cyclohexanone 38.7 38.7 38.7 38.7 38.7 38.7 38.7 Resin Adhesive 1 32.3 Resin Bonding Agent 2 32.3 Resin Adhesive 3 32.3 Resin Adhesive 4 32.3 Resin Adhesive 5 32.3 Resin Adhesive 6 32.3 Resin Adhesive 7 32.3 HELIOGEN BLUE D7086 0.021 0.021 0.021 0.021 0.021 0.021 0.021 Pariotol Yellow D0960 0.006 0.006 0.006 0.006 0.006 0.006 0.006 0.16 0.16 0.16 0.16 0.16 0.16 0.16 IXE-6107 0.82 0.82 0.82 0.82 0.82 0.82 0.82 SOC2 surface treated by KBM-573 16.0 16.0 16.0 16.0 16.0 16.0 16.0 DCP-A 5.3 5.3 5.3 5.3 5.3 5.3 5.3 YDF-170 2.9 2.9 2.9 2.9 2.9 2.9 2.9 Irgacure 907 0.6 0.6 0.6 0.6 0.6 0.6 0.6 DETX-S 0.005 0.005 0.005 0.005 0.005 0.005 0.005 EAB-F 0.019 0.019 0.019 0.019 0.019 0.019 0.019 Espel 1612 2.7 2.7 2.7 2.7 2.7 2.7 2.7 Megafac-F780F 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Meter 100 100 100 100 100 100 100 Inorganic filler solid content (% by mass) 40.0 40.0 40.0 40 .0 40.0 40.0 40.0 Coating viscosity (25°C) Ccp) 8.1 8.0 7.9 8.0 8.1 7.8 7.7 Film melt viscosity (30°〇(Pa · s) 6.3χ105 6.4x105 6_2χ105 6.0χ105 6.0χ105 7.5χ105 7.6χ105 Film melt viscosity (70°〇(Pa·s) 1.8χ103 1.9x103 1.8χ103 1·9χ103 1.8χ103 4.8χ102 4.5χ102 Buriedness Δ Δ Δ Δ Δ 〇〇TCT Δ Δ Δ Δ Δ 〇〇HAST Δ Δ Δ Δ Δ 〇〇 Solder heat resistance Δ Δ Δ Δ Δ 〇〇 analytical 〇〇〇〇〇〇〇-72-

S 201224663 [Table 2] Ingredient Example 1-8 1-9 1-10 1-11 Cyclohexanone 38.7 42.2 45.6 49.1 Resin Adhesive 6 32.3 26.9 21.5 16.2 HELIOGEN BLUE D7086 0.021 0.017 0.014 0.010 Pariotol Yellow D0980 0.006 0.005 0.004 0.003 Melamine 0.16 0.13 0.11 0.08 IXE-6107 0.82 0.69 0.55 0.41 Surface treated SO-C2 by KBM-573 20.0 24.0 28.0 Surface treated with KBM-573 B-30 16.0 DCP-A 5.3 4.4 3.5 2.6 YDF-170 2.9 2.4 1.9 1.4 Irgacure 907 0.6 0.5 0.4 0.3 DETX-S 0.005 0.005 0.004 0.003 EAB-F 0.019 0.016 0.013 0.010 Espel 1612 2.7 2.3 1.8 1.4 Megafac F-780F 0.2 0.2 0.2 0.1 100 100 100 100 Inorganic filler solid content (quality %) 40.0 50.0 60.0 70.0 Coating viscosity (25 ° C) (卬) 7.9 8.1 8.0 8.0 Film melt viscosity (30 ° 〇 (Pa. s) 6.2x10s _7·9 χ 105 1.8 χ 105 1.3x10s film melt viscosity (70.) (Pa. s) 1·9χ103 4.9xl02 8.6χ102 1.4χ103 Buriedness Δ 〇〇〇TCT Δ 〇〇〇HAST Δ 〇〇〇 Solder heat resistance Δ 〇〇〇 Analytical 〇〇〇〇-73- 201224663 [table 3]

Ingredient Comparative Example 1-1 1-2 1-3 1-4 1-5 1-6 1-7 1-8 Cyclohexanone 39.0 39.0 42.5 26.7 39.0 39.0 39.0 39.0 Resin Adhesive 1 32.3 Resin Adhesive 6 32.3 26.9 37.7 32.3 32.3 32.3 32.3 HELIOGEN BLUE D7086 0.021 0.021 0.017 0.024 0.021 0.021 0.021 0.021 Pariotol Yellow D0960 0.006 0.006 0.005 0.007 0.006 0.006 0.006 0.006 Melamine 0.16 0.16 0.13 0.18 0.16 0.16 0.16 0.16 IXE-6107 0.82 0.82 0.69 0.96 0.82 0.82 0.82 0.82 SO-C2 (No surface treatment) 16.0 16.0 20.0 12.0 SO-C2 surface treated by KBM-403 16.0 SO-C2 surface treated by KBM-903 16.0 SO-C2 16.0 surface treated by KBM-1003 by HMDS-3 Surface treatment of SO-C2 16.0 DCP-A 5.3 5.3 4.4 6.2 5.3 5.3 5.3 5.3 YDF-170 2.9 2.9 2.4 3.4 2.9 2.9 2.9 2.9 Irgacure 907 0.6 0.6 0.5 0.7 0.6 0.6 0.6 0.6 DETX-S 0.005 0.005 0.005 0.006 0.005 0.005 0.005 0.005 EAB-F 0.019 0.019 0.016 0.022 0.019 0.019 0.019 0.019 Espel 1612 2.7 2.7 2.3 3.2 2.7 2.7 2.7 2.7 Megafac-F780F 0.2 0.2 0.2 0.3 0.2 0.2 0.2 0.2 00 100 100 91 100 100 100 100 Inorganic filler solid content (% by mass) 40.0 40.0 50.0 30.0 40.0 40.0 40.0 40.0 Coating viscosity (25 ° C) (卬) 7.8 7.9 8.1 8.1 7.8 8.0 8.1 8.0 Film melt viscosity (30 °〇(Pa · s) Ι.ΟχΙΟ6 1.2χ106 2·〇χ106 δ.ΐχίο5 1.3χ106 1.2χ106 Ι.ΙχΙΟ6 1.4x106 Film melt viscosity (70°〇(Pa · s) 2.5χ103 2.9χ103 Ι.ΙχΙΟ4 4.6χ102 2.3 χΙΟ3 2.8χ103 2.6χ103 2.5 χ103 Buriedness XXX 〇XXXX TCT XX Δ XXXXX HAST Δ X Δ X Δ Δ Δ Δ Solder heat resistance Δ Δ Δ X Δ Δ Δ Δ Analytical XXX ' Δ XXXX -74-

S 201224663 Surfaces containing inorganic fillers according to the results shown in Tables 1-3

Solder heat resistance, coating film, and formed photosensitive coating film, thermal shock resistance (TCT), electrical insulation (hast), and cured film excellent in resolution can be applied to printed wiring boards and south density multilayer boards. And the manufacture of semiconductor packages and the like. Further, the right comparative example 1 - 1 ~ 丨 _ 丨 i and the comparative example 丨 丨 丨 丨 _ 8, although there is no large difference in the viscosity of the coating liquid, there is a large difference in the melt viscosity of the film. It is considered that this is because agglomeration occurs in the drying process of the coating liquid in Comparative Example 1 _丨~丨_8. (Example 2 series) The surface-treated fillers 7 to 12 were prepared as follows (Preparation Examples 7 to 12). (Preparation Example 7) Preparation of surface-treated filler 7 For 100 parts by mass of vermiculite particles (trade name: N s S - 4 N, manufactured by Tokuyama Co., Ltd., average particle diameter (d5 〇): 9 〇 nm), 1 part by mass of a decane coupling agent of the following structural formula (trade name: KBM-573, manufactured by Shin-Etsu Chemical Co., Ltd.) was subjected to a decane coupling treatment to prepare a surface-treated filler 7. a?CH3 NH-CH2CH2CH2-Si-〇CH3 〇ch3 (Preparation Example 8) Preparation of surface-treated filler 8 For 182 parts by mass of a filler (trade name: b-30, manufactured by Sigma Chemical Industry Co., Ltd., average particle diameter (d50) : 0.2μιη modulation), adding 1 part by mass

S-75- 201224663 Shi Xia coupling agent (trade name: KBM_573) was subjected to a decane coupling treatment to prepare a surface-treated filler 8. Further, B-30 (manufactured by Sigma Chemical Industry Co., Ltd.) having an average particle diameter (d50) of 〇.3 μΓη was pulverized to have an average particle diameter of 〇 2 μm. (Preparation Example 9) Preparation of surface-treated filler 9 For 100 parts by mass of vermiculite particles (trade name: NSS-4N, manufactured by Tokuyama Co., Ltd., average particle diameter (d5〇): 9 〇 nm), i parts by mass are added. The decane coupling agent of the structural formula (trade name: KB Μ-403, manufactured by Shin-Etsu Chemical Co., Ltd.) was subjected to a decane coupling treatment to prepare a surface-treated filler 9. Och3 CH2—&gt;CH-CH2-〇-CH2CH2CH2—Si—OCH3 〇OCH3 (Preparation Example 1 〇) Surface Treatment Filler 1 调制 Modulation For 100 parts by mass of vermiculite particles (trade name: NSS 4N, manufactured by Tokuyama Co., Ltd., The average particle size (d50): 9 〇 nm), i parts by mass of a decane coupling agent of the following structural formula (trade name: KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to perform a decane coupling treatment to modulate the surface. The filler 10 is treated. Och3 I 3 NH2—CH 2 CH 2 CH 2 —Si—OCH 3 OCH 3 (Preparation Example 11) Preparation of Surface Treatment Filler 11 For Shishishi particles with 100 mass damage (trade name: Tokuyama Co., Ltd., average particle diameter (d50): 90 nm) ,Add to! Parts by mass

-76- S 201224663 The following structural formula Shihisa coupling agent (trade name··ΚΒΜ-1 003, manufactured by Shin-Etsu Chemical Co., Ltd.) was subjected to a decane coupling treatment to prepare a surface treatment filler 11 for the surface. Och3

Ch^sCH-CH2-Si-OCH3 OCH3 (Preparation Example 12) Preparation of surface-treated filler 12 For 100 parts by mass of vermiculite particles (trade name: NSS-4N,

Ku 偶 制 To To To To To To To To To To To To To To To To To To To To To To To To To To To To To To To To To To To To To To To To To To To To To To To HM HM HM HM Coupling treatment, modulating surface treatment filler 12 〇ch3 ch3

CH3~Si-NH-Si-CH3 IIJ ch3 ch3 (Example 2-1) Except that in Example 1-1, the surface-treated filler 1' instead of the inorganic filler was used in addition to the surface-treated filler 7, and Example 1 In the same manner, the photosensitive composition coating liquid is prepared to prepare a photosensitive film, to prepare a laminate, and to form a permanent pattern. Further, the amount of the inorganic filler added was 16.0 parts by mass which was the same as that of Example 1-1. The measurement of the viscosity of the photosensitive composition coating liquid and the measurement of the melt viscosity of the photosensitive layer were carried out in the same manner as in Example 1 -. Further, in the measurement of the reliability test, in addition to the evaluation of the light transmittance (HAZE) described below in Example 1 _ 1

In the same manner as in Example 1-1 except for S-77-201224663, embedding property, thermal shock resistance (crack resistance) (TCT), insulation (HAST), solder heat resistance (weld-resistance), and Analytical evaluations. The results of these measurements are summarized and shown in Table 4 below. Evaluation of light transmittance (HAZE) - Evaluation of light transmittance (HAZE) The diffusion transmittance (Td) and total light transmittance of the photosensitive film were measured using Opto Design Inc. JCH-200S (trade name). Tt) 'Get the value of (Td/Tt)xl〇〇 and evaluate it with this value. Here, the lower the value, the higher the transparency. (Examples 2-2 to 2-7) In the example 2-1, in place of the binder resin oxime synthesized in the synthesis example, the binder resins 2 to 7 synthesized in Synthesis Examples 2 to 7 were used, as shown in the following table. In the same manner as in Example 2, the photosensitive liquid composition coating liquid was prepared in the same manner as in Example 2_丨, and the viscosity of the coating liquid was measured, and the photosensitive liquid film was produced in the same manner as in the actual yoke example 2-1. In the same manner as in the example, the measurement results of the guilty life scorpion are summarized and shown in Table 4 below. (Examples 2 to 8) In the examples 2 - 6, in the case of the treatment of the surface treatment filler 7 as a heat engine filler, the surface treatment 搐袓s ^ to the filling 8 ' is as follows As shown in Table 5, the photosensitive light was prepared in the same manner as in Example 2-6, and the coating liquid was taken down, and the coating liquid was measured, and the viscosity of the coating liquid was measured. Then, the coating liquid was used, and M was used. In Example 2_6, a photosensitive film was produced in the same manner as in Example 2-6, and the reliability was evaluated. Summarizing the results of these measurements is not shown in the following, +, + π &amp;, r 4 in Table 5.

S-78-201224663 (Examples 2-9 and 2-10) In the same manner as in Example 2-6 except that the photosensitive composition coating liquid was the composition ratio shown in Table 5 below. In the same manner as in Example 2-6, a photosensitive film was produced, and the coating liquid was used to measure the viscosity of the coating liquid. The reliability was evaluated in the same manner as in Example 2-6. The measurement scores of these are summarized and shown in Table 5 below. (Comparative Examples 2-1, 2-3, and 2-4) In Example 2-6, vermiculite particles (average particle diameter (d5〇) which were surface-treated with a non-decane coupling agent were used as the inorganic filler: 9 〇 nm ' NSS-4N, manufactured by Tok Uyama Co., Ltd.), as shown in the following Table 6, was prepared in the same manner as in Example 2-6, and the viscosity of the coating liquid was measured, and the coating liquid was used in the same manner as in Example 2 (6) A photosensitive film was produced in the same manner, and reliability evaluation was performed in the same manner as in Example 2-6. The results of these measurements are summarized and shown in Table 6 below. (Comparative Example 2-2) In Comparative Example 2_丨, instead of the binder resin 6 synthesized in Synthesis Example 6, the binder resin yt synthesized in Synthesis Example 1 was used, as shown in Table 6 below, and a comparative example. 2-1. The photosensitive composition coating liquid was prepared in the same manner, and the viscosity of the coating liquid was measured. Using the coating liquid, a photosensitive film was produced in the same manner as in Comparative Example 2_丨, and reliability evaluation was performed in the same manner as in Comparative Example 2-1. . The measurement results of these were discarded and are shown in Table 6 below. (Comparative Example 2 - 5 to 2 - 8) In Comparative Example 2 - 1 , instead of the surface treated with the non-decane coupling agent, the Shihashi particle (trade name: NS S-4N, Tokuyama Corporation _ I 1 average particle diameter) (d50): 90 rm), using the surface treatment prepared in Preparation Examples 9 to 12, -79-1, 201224663, 9 to 1 2, as shown in the following Table 6, the photosensitive composition was prepared in the same manner as in Comparative Example 2-1. The coating liquid was measured, and the viscosity of the coating liquid was measured. Then, a photosensitive film was produced in the same manner as in Comparative Example 2-1, and the reliability was evaluated in the same manner as in Comparative Example 2-1. The results of these measurements are summarized and shown in Table 6 below. (Comparative Example 2 - 9) In Example 2-1, the composition coating liquid of the composition of Example 2 in Table 1 of the paragraph "0 0 4 5" of JP-A-2003-234439 was prepared, and the coating was measured. In the same manner as in Example 2-1, a photosensitive film was produced in the same manner as in Example 2-1, and the reliability of the coating was evaluated in the same manner as in Example 2-1. The results of these measurements are summarized and shown in Table 7 below. -80-201224663 [Table 4] Ingredient Example 2-1 2-2 2-3 2-4 2-5 2-6 2-7 Cyclohexanone 38.7 38.7 38.7 38.7 38.7 38.7 38.7 Resin Adhesive 1 32.3 Resin Adhesive 2 32.3 Resin Adhesive 3 32.3 Resin Adhesive 4 32.3 Resin Adhesive 5 32.3 Resin Adhesive 6 32.3 Resin Adhesive 7 32.3 HELIOGEN BLUE D7086 0.021 0.021 0.021 0.021 0.021 0.021 0.021 Pariotol Yellow D0960 0.006 0.006 0.006 0.006 0.006 0.006 0.006 Melamine 0.16 0.16 0.16 0.16 0.16 0.16 0.16 IXE-6107 0.82 0.82 0.82 0.82 0.82 1 0.82 0.82 NSS-4N treated by KBM-573 16.0 16.0 16.0 16.0 16.0 16.0 16.0 DCP-A 5.3 5.3 5.3 5.3 5.3 5.3 5.3 YDF-170 2.9 2.9 2.9 2.9 2.9 2.9 2.9 Irgacure 907 0.6 0.6 0.6 0.6 0.6 0.6 0.6 DETX-S 0.005 0.005 0.005 0.005 0.005 0.005 0.005 EAB-F 0.019 0.019 0.019 0.019 0.019 0.019 0.019 Espel 1612 2.7 2.7 2.7 2.7 2.7 2.7 2.7 Megafac-F780F 0.2 0.2 0.2 0.2 0.2 0.2 0.2 100 100 100 100 100 100 100 Inorganic filler solid content (% by mass) 40.0 40.0 40.0 4 0.0 40.0 40.0 40.0 Viscosity of coating solution (25°〇(cp) 13.2 14.5 20.1 13.5 26.3 16.5 16.3 Film melt viscosity (30°C) (Pa · s) 6.3χ105 6.4χ105 6.2χ105 6.〇χ105 6.〇χ105 7.5χ105 7.6χ105 Film Melt Viscosity (70°C) (Pa · s) 2.1χ103 1.6χ103 2.〇χ103 1.5χ103 2.〇χ103 Ι.ΙχΙΟ3 Ι.ΟχΙΟ3 Buriedness Δ Δ Δ Δ Δ 〇〇TCT Δ Δ Δ Δ Δ 〇〇HAST Δ Δ Δ Δ Δ 热 Thermal Δ Δ Δ Δ Δ Δ 〇〇 HAZE 30 25 20 21 24 26 23

S -81 - 201224663 [Table 5] Ingredient Example 2-8 2-9 2-10 Cyclohexanone 38.7 42.2 49.1 Resin Adhesive 6 32.3 26.9 21.5 HELIOGEN BLUE D7086 0.021 0.017 0.014 Pariotol Yellow D0960 0.006 0.005 0.004 Melamine 0.16 0.13 0.11 IXE-6107 0.82 0.69 0.55 NSS-4N 20.0 24.0 surface treated with KBM-573 B-30 16.0 DCP-A surface treated with KBM-573 5.3 4.4 3.5 YDF-170 2.9 2.4 1.9 Irgacure 907 0.6 0.5 0.4 DETX -S 0.005 0.005 0.004 EAB-F 0.019 0.016 0.013 Espel 1612 2.7 2.3 1.8 Megafac-F780F 0.2 0,2 0.2 Meter 100 100 100 Solid content of inorganic filler (% by mass) 40.0 50.0 60.0 Viscosity of coating solution (25°〇(cp 16.8 17.1 19.1 Film Melt Viscosity (30°〇Pa (s) 5.5x10s 5.8x10s 6.5x10s Film Melt Viscosity (70°〇(Pa · s) 1.9χ103 1.2χ103 1.2χ103 Buried Δ 〇〇TCT Δ 〇〇 HAST Δ 〇〇 Solder heat resistance Δ 〇〇 Analytical 〇〇〇 HAZE 30 31 36

-82- S 201224663 [Table 6] Ingredient Comparative Example 2-1 2-2 2-3 2-4 2-5 2-6 2-7 2-8 Cyclohexanone 39.0 39.0 42.5 26.7 39.0 39.0 39.0 39.0 Resin Adhesive 1 32.3 Resin Adhesive 6 32.3 26.9 37.7 32.3 32.3 32.3 32.3 HELIOGEN BLUE D7086 0.021 0.021 0.017 0.024 0.021 0.021 0.021 0.021 Pariotol Yellow D0960 0.006 0.006 0.005 0.007 0.006 0.006 0.006 0.006 Melamine 0.16 0.16 0.13 0.18 0.16 0.16 0.16 0.16 IXE-6107 0.82 0.82 0.69 0.96 0.82 0.82 0.82 0.82 NSS-4N (without surface treatment) 16.0 16.0 20.0 12.0 20.0 12.0 NSS-4N 16.0 surface treated with KBM-403 NSS-4N 16.0 surface treated with KBM-903 via KBM-1003 surface Treated NSS-4N 16.0 NSS-4N 16.0 DCP-A surface treated with HMDS-3 5.3 5.3 4.4 6.2 5.3 5.3 5.3 5.3 YDF-170 2.9 2.9 2.4 3.4 2.9 2.9 2.9 2.9 Irgacure 907 0.6 0.6 0.5 0.7 0.6 0.6 0.6 0.6 DETX-S 0.005 0.005 0.005 0.006 • 0.005 0.005 0.005 0.005 EAB-F 0.019 0.019 0.016 0.022 0.019 0.019 0.019 0.019 Espel 1612 2.7 2.7 2.3 3.2 2.7 2.7 2.7 2.7 Megafac-F78 0F 0.2 0.2 0.2 0.3 0.2 0.2 0.2 0.2 100 100 100 91 100 100 100 100 Inorganic filler solid content (% by mass) 40.0 40.0 50.0 30.0 40.0 40.0 40.0 40.0 Coating viscosity (25 ° C) __(£^_ 56.2 64.2 76.8 52.1 51.3 62.3 64.1 64.1 Film melt viscosity (30 ° C) (Pa · s) Ι.ΟχΙΟ6 1.2x106 2.0χ106 8.1χ105 1.3χ106 1.2χ106 Ι.ΙχΙΟ6 1.4x106 Film melt viscosity (70°C) (Pa · s 6.5χ105 7.1χ105 9.8χ105 ό.ΙχΙΟ4 6.9χ105 7.2χ105 9.8χ105 9.5χ105 Buried XXX 〇XXXX _ TCT XX Δ XXXXX HAST Δ X Δ X Δ Δ Δ Δ Solder heat resistance Δ Δ Δ X Δ Δ Δ Δ Sex XXX Δ XXXX HAZE 75 62 82 73 73 85 81 80

S -83- 201224663 [Table 7] Ingredient Comparative Example 2-9 Bisphenol A type epoxy resin (EP828, Oiled Shell Japan) 10.0 Methyl hexahydrophthalic anhydride (B-650, Dainippon Ink Chemical Industry Company) 10.0 Micro-station hardener (2MZ-A, Shikoku Chemical Industry Co., Ltd.) 0.2 Polymer dispersant (Solsperse 24000, AVECIA Chemical Co., Ltd.) 0.4 Spherical vermiculite (S0-C2, Longsen) 20 Spherical Vermiculite (EB-6D, Electrochemical Industry Co., Ltd.) 60 Meter 101 Inorganic Filler Solid Content (% by mass) 79.5 Viscosity of Coating Solution (25°C) (cp) 8000 Film Melt Viscosity (30°C) (Pa · s Ι.ΙχΙΟ2 Film melt viscosity (70 °C) (Pa * s) 1.3x10' Buried X TCT X HAST Δ Solder heat resistance Δ Analytical X HAZE 90

S-84-201224663 According to the results of Table 4, the photosensitive filler having the inorganic filler partially structured as shown in the above formula (A) has a good dispersion. The coating, the coating suitability, and the application of the photosensitive coating on the surface, and the formed photosensitive coating film can provide embedding properties, thermal shock resistance (TCT), electrical insulation (hast), solder heat resistance, and resolution. The excellent high light transmittance cured film is suitable for the manufacture of printed wiring boards, high density multilayer boards, and semiconductor packages. 'If you compare the example 2 _ 1~2 -1 〇 with the comparative example 2 _ 1~2 - 9, although there is no big difference in the viscosity of the coating liquid, there is a big difference in the melt viscosity of the film. This is because in Comparative Example 2 _ 1 to 2 -9, agglomeration occurred in the drying process of the coating liquid. Here, the evaluation of the light transmittance (HAZE) of the photosensitive film produced in the Example 另-丨 was carried out. It was confirmed that Example 2-0 was more excellent than Example 1-1. [Industrial Applicability] The photosensitive composition of the present invention can be suitably used for a solder resist. The photosensitive film of the present invention can be applied to various pattern formations such as a protective film, an interlayer insulating film, and a permanent pattern such as a solder resist pattern, and a liquid crystal structure such as a color filter, a pillar, a rib, a spacer, or a partition wall. The manufacture of components, holograms, micromachines, manufacturing of verification, and the like are particularly applicable to the formation of permanent patterns on printed substrates. The pattern forming method of the present invention can be applied to various pattern forming, color filters, pillars, and ribs, such as a permanent pattern such as a protective film, an interlayer insulating film, and a solder resist pattern, by using the photosensitive composition ' Manufacturing, hologram, micro of liquid crystal structural members such as spacers and partition walls

S -85- 201224663 Machine, test, manufacturing, etc., especially suitable for permanent pattern formation on printed boards. The present invention has been described in connection with the embodiments of the invention, and the invention is not limited by the details of the invention, which is not limited to the details of the invention as set forth in the appended claims. I think that it should be interpreted broadly. This case is based on the special wishes of 20 1 0- 1 936 1 7 and the special wish 2 (H0-193627) of the patent application on August 31, 2010. BRIEF DESCRIPTION OF THE DRAWINGS [Brief Description of the Drawings] Fig. 1 is an explanatory view showing a layer constitution of a photosensitive film. [Description of main components] 1 Support 2 Photosensitive layer 3 Protective film

-86- S

Claims (1)

201224663 VII. Patent application scope: 1. A photosensitive composition comprising at least one inorganic filler, a binder, a photopolymerization initiator, and an inductive compound of a polymerizable compound, characterized in that: the photosensitive composition The content of the inorganic filler in the total solid content of the material is 30% by mass or more, and the particle surface of the inorganic filler has a partial structure represented by the following formula (A), -L, -NH-R2 · . In the formula (A), R2 represents an organic group having 1 to 12 carbon atoms, and Li represents an alkyl group having 1 to 12 carbon atoms. 2. The photosensitive composition of claim 1, wherein the inorganic filler has an average particle diameter (d5 0) of less than 0 3 μηη. 3. The photosensitive composition according to claim 1 or 2, wherein the surface of the filler-free particle has a partial structure represented by the following formula (Β)-Si(〇R,)2-Li-NH -R2 · · · Formula (B) In the formula (B), R represents a methyl group or an ethyl group, I represents an organic group of carbon number 〜, and 川 represents an alkylene group having a carbon number of 1-4 to 12; , 2 1 can each be the same or different. 4. The photosensitive composition according to claim 1 or 2, wherein the filler is treated by a decane coupling agent represented by the following formula (c), and the formula (C) ♦ 0R OR - 87- Filling the carbon filling machine 12 series and S 201224663, / 1 5 In the general formula (C), R represents a fluorenyl group or an ethyl group, and η means that the two R's are the same or Dissimilarity, 5 · The photosensitive composition of claim 1 or 2, wherein the β Hai inorganic filler is Shi Xishi. 6. The photosensitive composition according to claim 1 or 2, wherein the binder is a resin containing an acid group and an ethylenically unsaturated group, and is a polyurethane resin, an epoxy resin, and a polyfluorene. At least one resin selected from the group consisting of amines or polyimine resins. 7. The photosensitive composition according to claim 1 or 2, wherein the binder is a polyurethane resin containing an acid group and an ethylenically unsaturated group. 8. The photosensitive composition of claim 2 or 2, wherein the binder has a mass average molecular weight of 2, 〇〇〇~6〇, 〇〇〇, acid value is gKOHWgKOH/g, and B is not A saturated amine equivalent of 0.05 mmol/g to 3.0 mmol/g of a polyamine phthalate resin containing an acid and an ethylenically unsaturated group. 9. If you feel the sensation of the first or second patent scope, the zf is the hometown and the private agent is an acid group and an ethylenic unsaturated compound, which has the following formula: (1) ~(3) A urethane resin, one less, of the functional group to 0 II ^ -X-C R3 C=C r1 General formula (1) In the formula (1), R1 ~R3 each independently f-based, X represents an oxygen atom, a sulfur atom 啖M, a non-oxygen atom or a monovalent hydrogen atom or a monovalent organic group, &quot;, here, R12 201224663 ΐ f γ-c- c=c R1 R6 R7 Formula (2) In the formula (2), R4 to R8 each independently represent a hydrogen atom or a monovalent organic group, and Y represents an oxygen atom, a sulfur atom or -N(R12)-; , R12 is synonymous with R12 of the above formula (1), In the formula (3), R9 to RM each independently represent a hydrogen atom or a monovalent organic group; and Z represents an oxygen atom, a sulfur atom, -N(R13)- or a phenyl group which may have a substituent Here, R13 represents an alkyl group which may have a substituent. The photosensitive composition of claim 1 or 2, wherein the binder is a polyamine phthalate resin containing an acid group and an ethylenically unsaturated group, and has the following general formula (UG) Partial construction shown, general formula (UG), ch2 Ο II t —NH—C-0 In the general formula (UG), R1 to R3 each independently represent a hydrogen atom or a monovalent organic group, A represents a divalent organic residue, and X represents an oxygen atom, a sulfur atom or -N(R12)-; here, R12 Represents a hydrogen atom or a monovalent organic group. -89- 1 201224663 1 1 - The photosensitive composition of claim 1 or 2, wherein the binder is a polyurethane resin containing an acid group and an ethylenically unsaturated group, and is a diisocyanate compound a reaction product with at least two kinds of diol compounds, at least one of which is (1) has an ethylenically unsaturated group, and at least one of the hydroxyl groups is a diol compound of a secondary alcohol, and At least one diol compound having a carboxyl group (2). The photosensitive composition of claim 11, wherein the (1) has a ethylenically unsaturated group, and at least one of the hydroxyl groups is a secondary alcohol diol compound, which is represented by the following formula (G) ) the compound shown, general formula (G) ΓΗ ^〇H Hi/ 2, CH I In the general formula (G), R1 to R3 each independently represent a hydrogen atom or a monovalent organic group, A represents a divalent organic residue, and X represents an oxygen atom, a sulfur atom or -N(R12)-; here, R12 Represents a hydrogen atom or a monovalent organic group. A photosensitive composition according to claim 1 or 2, which further contains a thermoplastic elastomer. 14. The photosensitive composition of claim 13, wherein the thermoplastic elastomer system comprises a styrene elastomer, an olefin elastomer, an urethane elastomer, a polyester elastomer, and a polyamine. At least one elastomer selected from the group consisting of an elastomer, an acrylic elastomer, and a polyoxynene elastomer. -90- 201224663 1 5 . A kind of photosensitive enamel film, which has a photosensitive layer on the support, and the photosensitive layer is made up of, for example, 申谙直&amp; _月I利 range 1 to 1 Among the four items, it consists of a photosensitive composition. 1 6. A photosensitive film characterized by having a photosensitive layer formed of a photosensitive composition, the photosensitive layer containing an inorganic filler, the surface of the inorganic filler having the following general formula Partial structure shown in (A) The content of the inorganic filler in all the solid components of the photosensitive composition was 30 mass. /〇, the photosensitive layer has a melt viscosity of 30 cc or more at 30 C, and the photosensitive layer has a melt viscosity at 7 ° C. When the average particle diameter of the inorganic filler is less than 0.3 μm, it is 5 x 1 〇3Pa.s or less, when the average grain size of the inorganic filler is 〇.3μηη or more, it is 2xi〇3pa.s or less, -L, -NH-R2 · · · Formula (a) Formula (a) t ' R2 represents an organic group having a carbon number of 丨 12 and 12 and represents an alkylene group having 1 to 12 carbon atoms. The photosensitive film of claim 16 wherein the inorganic filler has an average particle hollow (d 5 0) lower than 〇. 3 μπι. The photosensitive film of claim 16 or 17, wherein the photosensitive layer contains the inorganic filler together with at least one of a binder, a photopolymerization initiator, and a polymerizable compound. The photosensitive film of claim 16 or 17, wherein the content of the inorganic filler in all the solid components of the photosensitive composition is 50% by mass or more. S-91-201224663. The photosensitive film of claim 16 or 17, wherein the particle surface of the inorganic filler has a partial structure represented by the following formula (B): • -Si(ORi)2-L1-NH-R2 In the formula (B), a methyl group or an ethyl group, 112 represents an organic group having 1 to 12 carbon atoms, and 1^ represents an alkyl group having 1 to 12 carbon atoms. Here, two 1^ can each be the same or different. 2. The photosensitive film according to claim 16 or 17, wherein the inorganic filler is treated by a decane coupling agent represented by the following formula (C), wherein the formula (C) OR I Si-OR I OR In the formula (C), R represents a methyl group or an ethyl group, and η represents an integer of 1 to 5; here, each of the three R groups may be the same or different. 22. The photosensitive film of claim 16 or 17, wherein the inorganic filler is vermiculite. 23. The photosensitive film of claim 18, wherein the adhesive is a resin containing an acid group and an ethylenically unsaturated group, and is a polyurethane resin, an epoxy resin, and a polyamine. Or at least one resin selected from the group consisting of polyimide resins. 24. The photosensitive film of claim 18, wherein the binder is a polyamine phthalate resin containing an acid group and an ethylenically unsaturated group. S-92· 201224663 2 5 . Photosensitive film of claim 18, wherein the binder has a mass average molecular weight of 2, 〇00~6〇, and an acid value of 2〇111§&amp;; 011 / L ~ 120mgKOH / g, ethylenically unsaturated group equivalent of 0.05mmol / g ~ 3.0 mmol / g of acid-containing and ethylenically unsaturated group of polyamine phthalate resin 2 6. As claimed in the scope of patent 1 8 of the soil &amp; beta shell of the precursor film, wherein the binder is containing acid groups and ethylenically unsaturated groups + / 丨 people, K. Polyurethane resin, and contains in the side chain At least one of the functional groups represented by the following general formula (1) to 〇, J In the formula (1), R to W each independently represent a group, and X represents an oxygen atom or a sulfur atom. Also, it means that a hydrogen atom or a monovalent atom has a hydrogen atom or a monovalent organic group, or ·N(R12)-; here, R12 In the general formula (2), each of R and R8 is represented by an organic group, and an electron atom and an anthracene. It means that the hydrogen atom or the monovalent group has the same meaning as the above formula (1), or -N(R12)-; here, the R12 system S -93- 201224663 wherein 'R9 to R&quot; each independently represents a hydrogen atom or a monovalent organic group 'Z represents an oxygen atom, a sulfur atom, -N(R13)- or a phenyl group which may have a substituent; Here, R13 represents an alkyl group which may have a substituent. 27. The photosensitive film of claim 18, wherein the binder is a polyamine phthalate resin containing an acid group and an ethylenically unsaturated group, and has a moiety represented by the following formula (UG) Structure, general formula (UG) Ο Λ , II /CH2 -NH—C—Ο, Ο II Q—C—NH—XH Human, Ο, R1 R3, C, R2 In the general formula (UG), Ri~R3 are each Independently, a hydrogen atom or a monovalent organic group 'A represents a divalent organic residue, and X represents an oxygen atom, a sulfur atom or _N(Rl2). Here, R12 represents a hydrogen atom or a monovalent organic group. 28. The photosensitive film according to claim 18, wherein the adhesive is a polyurethane resin containing an acid group and an ethylenically unsaturated group, and is a diisocyanate compound and at least two Reaction product of the diol compound 'At least one of the at least two diol compounds (1) has a ethylenically unsaturated group, and at least one of the hydroxyl groups is a diol compound of a secondary alcohol' (2) A diol compound having a carboxyl group. The photosensitive film of claim 28, wherein the (1) has a ethylenically unsaturated group, and at least one of the hydroxyl groups is a diol compound of a secondary alcohol. Is a compound represented by the following formula (G), 201224663 Formula (G) R3〆. In the general formula (G), R1 to R3 each independently represent a hydrogen atom or a monovalent organic group, A represents a divalent organic residue, and X represents an oxygen atom, a sulfur atom or -NCR12)-; here, R12 represents A hydrogen atom or a monovalent organic group. A photosensitive film according to claim 16 or 17, which further contains a thermoplastic elastomer. The photosensitive film of claim 30, wherein the thermoplastic elastomer system comprises a styrene elastomer, an olefin elastomer, an urethane elastomer, a polyester elastomer, and a polyamide elastomer. At least one elastomer 3 selected from the group consisting of an acrylic elastomer and a polysiloxane elastomer. 2. A method for forming a permanent pattern, which is characterized by the photosensitive composition of any one of claims 1 to 14. The object was applied to the surface of the substrate, dried, and the photosensitive layer was laminated to form a laminate, and then exposed and developed. 33. A permanent pattern characterized by being formed by a permanent pattern forming method as disclosed in claim 32. A printed circuit board characterized by being formed into a permanent pattern by a permanent pattern forming method according to claim 32 of the patent application. S -95-