TW201209066A - Photosensitive composition, photosensitive film, photosensitive laminate, method of forming permanent pattern, and printed board - Google Patents

Abstract

The present invention provides a photosensitive composition comprising an alkali-development resin, a polymeric compound, a photo polymerization initiator and a thermo crosslinking agent, in which the alkali-development resin is a polyurethane resin linking by an urethane group; there is at least one carboxy group on the end of the main chain and an ethylenic unsaturated group on the side chain of the polyurethane resin.

Description

201209066 6. Technical Field of the Invention The present invention relates to a photosensitive composition suitable as a solder resist material, a photosensitive film, a photosensitive laminate, a permanent pattern forming method, and a printed substrate. . [Prior Art] Conventionally, when a permanent pattern such as a solder resist is formed, a photosensitive film which is coated with a photosensitive composition on a support and dried to form a photosensitive layer is used. In the case of forming a permanent pattern of a solder resist or the like, it is known to laminate a photosensitive film on a substrate on which a permanent copper-clad laminate or the like is formed to form a laminate, and to expose the photosensitive layer of the laminate. Thereafter, the photosensitive layer is developed to form a pattern 〜, and then a hardening treatment or the like is performed to form a permanent pattern. In the photosensitive composition using the polyaminocarbamate (tetra) lipid as the adhesive of the above-mentioned solder resist, it has become important to improve the hardness and the like. · = For example, the patent document discloses that a polymerizable composition is suitable as a negative-type image-receiving layer having a high-molecular-weight/smoothing property and excellent image-forming property as a polyurethane-containing resin. Image recording of green material 又 Further, Patent Document 2 discloses a resin composition, which is suitable for use as a solder resist by using a polyamine phthalate resin as a binder. In addition to the high functionality of the products (including printed wiring boards, printing plates, and permanent pattern factories) that are carried by the photosensitive composition, the inventors have not repeatedly researched 201209066 photosensitivity. The composition of the composition requires further fine pattern shape; and the techniques described in the prior art documents are difficult to shape, and various characteristics such as development residue removal, heat resistance, toughness, steepness and insulation are also known. We do not expect to be able to fully satisfy the current situation and look forward to further improvement and development. [PRIOR ART DOCUMENT] [Patent Document] [Patent Document 2] JP-A-2005-250438 [Patent Document 2] JP-A-2006-243563 SUMMARY OF INVENTION [Problems to be Solved by the Invention] The present invention is related to In view of the current situation, the subject is to solve the problem and to achieve the following objectives. In other words, the present invention provides a photosensitive composition which has high development residue removability, can form a fine pattern, and is excellent in rain strength, resolution, and insulation; a photosensitive film of a photosensitive composition; and a photosensitive laminate. Body; odd formation method; and printed substrate. [Means for Solving the Problem] In the photosensitive composition containing an alkali-developable resin, a polymerizable compound agent, and a thermal crosslinking agent, it is found that an amine-bonded polyaminocarbamic acid (tetra) grease is used as the alkali developability. In the case where the aforementioned polyaminocarbamic acid (tetra) lipid has a radical to the terminal of the main chain and an ethylenically unsaturated group in the side chain, it is suitable and provides good developability.曰 Sex. However, in the case of the micrograph and the analysis, the conventional I provides the heat, the use of the long-form pattern, the result of the initial acid ester group, and the first carboxy-purification trans-4 - 201209066. The above findings regarding the means for determining the above-mentioned problems are as follows. In other words, the photosensitive composition is characterized in that it contains a photosensitive composition of an alkali-developable lipid, a polymerizable compound, a photopolymerization initiator, and a thermal crosslinking agent, wherein the alkali-developing resin is used. The amino phthalic acid vinegar resin which is bonded by a urethane group has at least one carboxyl group at the main terminal of the polyamino phthalate resin, and has an ethylenic unsaturated group in the side chain. The photosensitive composition according to the above-mentioned <1>, wherein the carboxyl group resin has two or more and five or less carboxyl groups at the terminal end of the polyurethane resin &lt;3&gt; as described above &lt;丨&gt; The photosensitive composition according to any one of the above-mentioned items, wherein the terminal of the main chain of the polyurethane resin has a structure represented by the following formula (I). -Ll-(CO〇H)n... General formula (1) 准' In the general formula (I), Li represents an organic chain of (n+1) valence, and η represents an integer of 1 or more. The photosensitive composition described in any one of the above-mentioned <1>, wherein the developable resin has an alkali developability having a carboxyl group in a chain of the polyamino phthalate resin. unit. The photosensitive composition described in <4>, wherein the alkali-developing monoterpene is represented by the following Rf-formula (II). \ 〒一 y - General (η) C〇〇H ; Decomposing dendrimers and bases form a singularity 201209066 However, in the general formula (π), Ri represents a hydrogen atom or an alkyl group, r2 and R3 Each of the groups: independently representing a single bond, an alkyl group having an ether group, a acetoxy group, a decylamino group, a carbon I Sa group, and an extended aryl group having a carbonate group. The photosensitive composition described in any one of the above-mentioned items, wherein the alkali-developable resin has a structural unit represented by the following general formula (νι).

However, in the above general formula (VI), X represents a direct bond, _CH2, C(CH3)2·, _S〇2_s_, CQ, or 〇·γ represents Jane, 眶〇, -NHCOO-, -CONH-, Or -OCONH-. The R groups may be the same or different from each other' each represents a hydrogen atom, a dentogen =, -OR15, -N(R16)(R17), or -SR18, and R15 and R18 represent a hydrogen atom or a monovalent organic group. &lt;7&gt; The photosensitive composition contained in the above-mentioned &lt;1&gt; to &lt;6&gt;, which is contained in the B, and has an ethylenically unsaturated group. (meth) propylene oxime

R, R13 and R are organic groups,

R

R &lt;8&gt; As described above, the photosensitive composition of the above-mentioned <br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br> The chain end is introduced into a carboxylic acid compound having at least i carboxyl groups. &lt;9&gt; The subtractive group of the above-mentioned &lt;丨&gt; to &lt;8&gt; τ drinking item, wherein the alkali-developable resin is _s prepared&quot;, 201209066, and has at least丨 ' ' &lt; n 〇 如 如 “ “ “ “ “ “ “ “ 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合 聚合The compound is a &lt;1〇&gt; oxime ester compound, which is an aromatic &quot;, 'sexual composition, #中中-isocyanide &lt;12&gt; such as a 4-system diisocyanate brewing compound. 12&gt; As described above, the photosensitive composition described in the item [00] is 5,0 〇〇 to 60, 〇00. The average molecular weight of the weight is &lt;1 3 &gt; <1> to <12>, which is characterized in that it has a photosensitive &lt;14> photosensitive laminate including a photosensitive composition as described in the above item, wherein the above &lt; The layer 0 of any one of 1&gt; to &lt;12&gt; is characterized in that it has a photosensitive &lt;1 5&gt;# permanent pattern forming method containing a photosensitive composition as a carrier, The photosensitive layer formed by the photosensitive composition as described in any one of &lt; 1 &gt; to &lt; 1 2&gt; is exposed to at least one of the characteristics of the photosensitive layer formed by the photosensitive composition described in any one of &lt; 1 &gt; It is characterized in that a permanent pattern is formed by the permanent pattern forming method described in the above <5>. [Effect of the Invention] According to the present invention, it is possible to solve the various problems of the prior art, and it is possible to provide a development residue removal property. a photosensitive composition having a fine pattern and excellent in heat, toughness, analytic property, and insulating property, a photosensitive film using the photosensitive composition, a photosensitive laminate, a permanent pattern forming method, and a printing method [Library of the invention] [Description of the invention] (Photosensitive composition) The photosensitive composition of the present invention contains a genus, a compound, a photopolymerization initiator, and a thermal crosslinking agent. The resin is obtained by further containing one component in one step. It is required to have a &lt;alkali-developable resin&gt; polyamino phthalate resin, and at the end of the above-mentioned polyamine One less carboxyl group and one side of a terephthalate tree group. Hardly having an ethylenic group - a carboxyl group at the end of the main chain - at the main hard end of the aforementioned polyamino phthalate resin, 1 female 21 1 carboxyl group preferably has ' 2 or more 5 points with excellent properties of eight to twenty-eight*, fine pattern formation, special soil, base '^ horse has 2 | and 'discussed polyurethane resin J&lt; main chain end Although two carboxy groups are preferred, but preferably at least one of the carboxy groups at the single ends may have at least one carboxyl group at both ends. The main chain end of the polyaminophthalic acid resin preferably has a structure represented by the general formula (1). Ι^-((:〇〇Η)η ··. General formula (I) However, in the above general formula (1), L1 represents an organic chain of (η+1) valence, and an integer of η表和1 or more Preferably, it is 1 to 5, and particularly preferably 2. The organic linking group represented by L1 is formed by polymerization of one or more atoms selected from a carbon atom, a sub-oxygen atom, a nitrogen atom, and a sulfur atom. The main one is saturated with one developing group. There is also a lower hydrogen atom. In addition, 201209066 Specifically, the number of atoms of the main skeleton constituting the organic linking group represented by L1 is preferably from 1 to 30, more preferably from 1 to 25. Further, it is more preferably 1 to 20, and particularly preferably 1 to 1 〇. Further, "the main skeleton of the organic linking group" means that only the L2 and the terminal C〇〇h are used in the general formula (ΠΙ) described later. An atom or a group of atoms, when there are a plurality of species in the meantime, means an atom or a group of atoms constituting the route having the least number of atoms used. A method of introducing at least one carboxyl group at the end of the main chain of the above-mentioned polyurethane resin It is not particularly limited and may be appropriately selected according to the purpose, and for example, a carboxylic acid compound having at least one carboxyl group may be used. A method of producing a raw material of a polyurethane resin, etc. - a carboxylic acid compound - the carboxylic acid compound is a monocarboxylic acid compound having one carboxyl group, and a dicarboxylic acid compound having two carboxyl groups. A tricarboxylic acid compound having three carboxyl groups, a tetracarboxylic acid compound having four carboxyl groups, a pentacarboxylic acid compound having five carboxyl groups, etc. Among these, in terms of excellent developability and fine pattern formability The carboxylic acid compound is not particularly limited as long as it has at least one basis, and may be appropriately selected according to the purpose, and is preferably the following: (III) The compound represented by the formula: Η—〇—L2—L^COOH)n—the general formula (m): In the above general formula (III), L1 and η represent the same meaning as the above-mentioned general formula. . 201209066 In the above general formula (m), l2 represents a single bond or a stretchable group which may have a substituent. The alkylene group having a carbon number of 1 to 2 Å is preferably an alkylene group having 2 to 10 carbon atoms in terms of the above alkylene group. Examples of the substituent which can introduce the alkylene group include a halogen atom (_F, _Br, 0, -1), an alkyl group which may have a substituent, and the like. The carboxylic acid compound represented by the above formula (m) is not particularly limited, and may be appropriately selected according to the purpose, and examples thereof include lactic acid, apple sir, hydroxycaproic acid, citric acid, a diol compound, and an acid. When used alone, it is also possible to use two or more kinds of m in combination, and it is particularly preferable to be malic acid. The reaction product of the above diol compound and the acid hydrazine may, for example, be a compound represented by the following structural formula. 〇

HOOC

(T^0H COOH fly. vfvwOH hoocXX°〇h cooh Clf0H COOH hooc^^〇A° 0 cf0H • Ethylene-unsaturated group _ Amino-based succinyl ester resin is on the side as a polyether of the test-developing resin The above-mentioned ethylenically unsaturated group is not particularly limited, and may be appropriately selected according to the purpose, and examples thereof include a vinyl group and the like. The functional group may, for example, be an acrylonitrile group, a mercapto propylene group, an acrylamide group, a mercapto acrylamide group, a vinyl phenyl group, a vinyl ester group, a vinyl ether group, an allyl ether. In the above, the crosslinked cured film forms a point of I·sheng and 5 is particularly preferably a methacryl fluorenyl group or an acryl fluorenyl group. The method of introducing an ethylenically unsaturated group into the side chain of the ester resin is not particularly limited, and may be appropriately selected according to the purpose, and for example, a diol compound having an ethylenically unsaturated group in a side chain may be used as the polyamino group. a method of producing a raw material for an acid ester resin, etc. The diol compound containing an ethylenically unsaturated group is not particularly limited and may be appropriately selected according to the purpose, and may be, for example, a commercially available product such as dimethylolpropane monoallyl ether or a halogenated diol. a compound such as a compound, a triol compound, an amino diol compound, or the like, and a compound containing an ethylenically unsaturated group such as a slow acid, an acid vapor, an isocyanate, an alcohol, an amine, a thiol or a dentated alkyl compound. The diol compound having an ethylenically unsaturated group in the side chain is not particularly limited, and may be appropriately selected according to the purpose, and for example, JP-A 20 0 5-25 The compound described in paragraph 043, No. 043, 〇〇 060 0060, and the following paragraphs [0064] to [0066] of JP-A-2005-25 0438, which is represented by the following general formula (G). In the above, the compound described in paragraphs [0064] to [〇〇66] of JP-A-2005-250438, which is represented by the following general formula (G), is preferred. -11- 201209066

OH

General formula (G) Atom, base. Especially have a base. It is not possible to have r3XVr2. However, in the above general formula (G), each independently represents hydrogen or a monovalent organic group, A represents a divalent organic residue, and represents an oxosulfide atom or -N(R'-, the aforementioned R12 The hydrogen atom or the monovalent organic group is not particularly limited as far as the Ri-valent organic group in the above general formula (G), and may be appropriately selected according to the purpose, and examples thereof include an alkyl group which may have a substituent. In the general formula (G), R is preferably a hydrogen atom or a group, and the monovalent organic group of R2 and R3 in the above general formula (G) is particularly limited, and may be appropriately selected according to the purpose. For example, an alkyl group having a substituent, etc., R2 and R3 in the above general formula (G) are preferably a hydrogen atom. As far as the A in the general formula (G) is described, 'as long as it is a divalent organic residue , the case base, the extension is not particularly limited 'can be selected according to the purpose, can be given - Goco -, the two-valent extension of the substituents, etc.. The above-mentioned two-valent organic residue, specifically, for example, Further, it is preferably an anthracenylene group. The above-mentioned general formula (9) is preferably an oxygen atom. In the above-mentioned general formula (G), the monovalent organic group of R12 is particularly limited, and may be appropriately selected according to the purpose, and examples thereof include an alkyl group having a substituent. Preferably, it is a mercapto group or an ethyl propyl group. Specific examples of the compound represented by the above general formula (G) are as follows, and are not shown. -13- 201209066

-14- 201209066

-15- 201209066

HO 丫 n

Ws ~. Further, the ethylene unsaturated group is not particularly limited in the amount of the polyurethane introduced, and may be appropriately prepared according to the purpose, and may be suitably used as an ethyl group, and 5' is O.OSmmol/g to 3.0 mmol/g. More preferably, 2 mmol/g to 2.7 mmol/g is particularly preferred as 55 mmol/g~:. - Alkali developability unit - The polyamine phthalate tree as the alkali-developable resin contains an alkali developable unit having a slow group in the side chain. The choice of the resin is preferably as follows: .5 mm ο 1 / g of the fat is preferably -16 - 201209066. The element is suitably selected for the alkali developable unit and t * 〇, preferably the lower system is not particularly Restriction, the general formula (Π) can be expressed according to the list R1

COOH

The general formula (1D, 1谇, and R3) also means that the single bond is a ^11 atom or a burnt group, the R2 group, the carbonic acid s group is stretched, and the s-base or the amine can be used. In the above formula (II), an alkyl group having a sulfonic acid sulfenyl group may be appropriately selected, for example, a methyl group, an ethyl group, a propyl group, etc. The alkyl group of R is not particularly limited, and is preferably The number of carbon atoms is from 1 to 10, and the substituent of the alkyl group, the acetyl group, the acetyl group, and the like can be introduced by way of example. For example, Nanyuan is suitable for the above general formula (II), R2n ^ :=. Selection: == For example 2, such as sub-3 methyl group, ethyl group, propyl group, butyl group, etc., ...... g. The aryl group is not particularly limited, and can be k and k according to the purpose, Preferably, the number of carbon atoms is from 6 to 15, and examples thereof include a stretching phenyl group, etc. The method for the side chain of the t-glycolic acid sl resin is not particularly limited, and may be suitably used in the side chain according to the purpose. The diol compound having a carboxyl group is a raw material for producing a polyurethane resin. The diol compound having a carboxyl group in a side chain is exemplified as follows. A compound represented by the general formula (IV). Example -17- 201209066 Η—. Q———·|_4 —〇*~—η - ι f

Ls - General (IV)

I (COOH)n However, in the above general formula (IV), z represents an atom having a valence of 3 or more. The L3 and L4 groups each independently represent a single bond or a stretchable group which may have a substituent, and both of L3 and L4 are not a single bond. B 5 indicates a single bond or a link base ^ Γι indicates an integer from 1 to 5. In the above general formula (IV), Ζ represents an atom having a valence of 3 or more. The atom having three or more valences as described above may, for example, be a nitrogen atom, a carbon atom or a ruthenium atom. Among these, a nitrogen atom or a carbon atom is particularly preferred. Here, the atom represented by ζ is not less than 3 valence means that at least ruthenium has three bonding hands bonded to the terminal end - COOH via L3, L4 and L5, and further has a gas atom or a substituent. The substituent which may be introduced into the oxime may be a substituent composed of an atom selected from a hydrogen atom, an oxygen atom, a sulfur atom, a nitrogen atom and a halogen atom. Among these, a hydrocarbon group having a carbon number of U0, more preferably a hydrocarbon group having 1 to 40 carbon atoms, and particularly preferably a hydrocarbon group having a carbon number of U0. In the foregoing general formula (IV). And the L4 series each independently represent a single bond or a substituent base which may have a substituent, and is not a single bond. The alkylene group is preferably an alkyl group having a carbon number of 丨 to "alkyl", more preferably a carbon atom number of 2 to 1 Å. The substitution m which can be introduced into the above-mentioned stretching group is, for example, a (four) child. (...&quot;, a base which may have a substituent, and a special one. -18 - 201209066 In the general formula (IV), 'L5 represents a single bond or a linking group. The linking group represented by L5 may be selected from a linking group composed of one or more kinds of atoms of a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom, and a sulfur atom. Specifically, the number of atoms of the main skeleton constituting the linking group represented by L5 is preferably from 1 to 30. Further, in the present invention, the "main skeleton of the linking group" is used only for connecting the above-mentioned general formula (IV). The atom or atomic group of Z and the terminal c〇〇H, when there are plural kinds of linking routes, the number of atoms used refers to the atom or atomic group constituting the least route. For the above diol compound having a carboxyl group in the side chain, there is no It is particularly limited and can be appropriately selected according to the purpose, and for example, 3,5-dihydroxyan Salicylic acid, 2,2-bis(hydroxymethyl)butyric acid (1)]^3 VIII), 2,2-bis(hydroxymethyl)propionic acid (DMPA), 2,2-bis(2-perylene) Ethyl)propionic acid, 2,2.bis(3-hydroxypropyl)propionic acid, bis(hydroxyindenyl)acetic acid, acetic acid, 2,2-bis(glycosyl)butyric acid, 4,4- Bis / tartaric acid, N, N-dihydroxyethylglycine, kn-bishydroxyethyl b 3 - carboxy-propionamide, and the like. These may be used alone or in combination of two or more. Particularly preferred are 2,2-bis(hydroxymethyl)butyric acid (DMBA) and 2,2-bis(hydroxyindenyl)propane. Acid (〇1\/1? eight). The content of the alkali-developable unit represented by the general formula (II) in the aforementioned polyaminocarboxylic acid S-reactive resin is not particularly limited, and the total structural unit of the polyurethane resin is #100m〇ly In the case, the developability unit represented by the above general formula (η) preferably contains 8 layers. 1% or less, more preferably 2 mol% to 70 mol%. -19-201209066 The alkali-developable resin having at least one carboxyl group at the end of the main chain and having an ethylenically unsaturated polyurethane resin in the side chain can be polymerized by, for example, a diol compound, An isocyanate compound and a carboxylic acid compound having at least one carboxyl group are obtained. - diol compound - The diol compound is not particularly limited and may be appropriately selected according to the purpose, and examples thereof include a polyether diol compound, a polyester diol compound, a polycarbonate diol compound, and a carboxyl group. A diol compound, a diol compound having an ethylenically unsaturated group in a side chain, and the like. These may be used alone or in combination of two or more. The polyether diol compound is not particularly limited, and may be appropriately selected according to the purpose, and examples thereof include the compounds described in paragraphs [0068] to [0076] of JP-A-2005-250438. Specifically, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, octaethylene glycol, di-1,2-propylene glycol, tri-1 , 2-propanediol, tetra-1,2-propanediol, hexa-1,2-propanediol, di-1,3-propanediol, tri-1,3-propanediol, tetra-1,3-propanediol, bis-1,3 -butanediol, tri-1,3-butanediol, hexa-1,3-butanediol, polyethylene glycol having a weight average molecular weight of 1000, polyethylene glycol having a weight average molecular weight of 1,500, weight average molecular weight of 2000 Polyethylene glycol, polyethylene glycol having a weight average molecular weight of 3,000, polyethylene glycol having a weight average molecular weight of 7,500, polypropylene glycol having a weight average molecular weight of 400, polypropylene glycol having a weight average molecular weight of 700, and polypropylene glycol having a weight average molecular weight of 1,000 A polypropylene glycol having a weight average molecular weight of 2000, a polypropylene glycol having a weight average molecular weight of 3,000, a polypropylene glycol having a weight average molecular weight of 4,000, or the like. -20- 201209066 The polyester diol compound is not particularly limited, and may be appropriately selected according to the purpose, and for example, paragraphs [0077] to [〇〇79] of the Japanese Patent Laid-Open Publication No. 2005_25〇438, In the paragraphs [〇〇83] to [〇〇85], the compounds described in No. 1 to Νο·8 and No. 13-No. 18 are used. The polycarbonate diol compound is not particularly limited and may be appropriately selected according to the purpose, and examples thereof include paragraphs [0080 Η 〇〇 8丨] and paragraphs [〇〇84] of JP-A-2005-250438. a compound or the like described in No. 9 to No. 12. The diol compound having an ethylenically unsaturated group in the side chain is the same as the diol compound having an ethylenically unsaturated group in the side chain described in the above ethylenically unsaturated group. The diol compound having a carboxyl group may, for example, be represented by the above general formula (IV). When the above-mentioned urethane resin is obtained, a diol compound having a substituent which does not react with an isocyanate group may be used in combination with the above diol compound. The diol compound having a substituent which does not react with the above-mentioned isocyanate group is particularly limited, and can be appropriately selected according to the purpose, and for example, Japanese Patent Laid-Open Publication No. 2005-250438 Paragraph [〇〇87] ~ [0088] 兮W. Compounds that have been planted, etc. Further, in the synthesis of the 1 t urethane resin, in addition to the above diol compound, a compound obtained by ring-opening a tetrabasic acid dianhydride with a diol compound may be used in combination. There is no particular limitation on the compound in which the tetracarboxylic acid dianhydride is opened by a diol compound, and it can be appropriately selected according to the purpose, and it can be exemplified in paragraph [0095] of the Japanese Patent Publication No. -200109066. Special opening 2 0 0 5 - 2 5 0 4 3 8 [Ο 1 Ο 1] The compound described herein. - Diisocyanate compound _ The above-mentioned diisocyanate compound is appropriately selected according to the purpose, and is preferably a diisocyanate compound or the like which can be represented by a temple. The column is as follows: (V) 〇CN-L6-Nc〇 However, in the above general formula (V), 1 represents a valency aliphatic or aromatic hydrocarbon group. L6 optionally has a complex i f A^ t having a substituent of 2 ester groups, and may have a group other than isocyanate, such as an ester group, an amine group, or a urea group. * The formate base and hydrazine are described in the general formula (v). There is no special protection against A-iso- ate compound, and you have special restrictions. You can choose according to the target > The poly(VI)-kappa urethane resin which can be described as an alkali-developable resin contains a point which is generally the following (v υ υ , , , , , , 。 。 。 。 。 。 。 。 。 。 。 。 For the following three general expressions (VI)

(3) 2, -S02-, -S-, -CO-, or β Υ means _ΝΗ_

-NHCO- , -NHCOO- ' -CONH or -OCONH-. R1

-22- 201209066 R, 3 and R14 are mutually identical or non-organic, tooth atom, _0R15, represents a hydrogen atom, -valent R16HRu 矣n ), or - sr18; r15, R represents a hydrogen atom or a valence organic From the viewpoint of developability, the above: particularly preferably -CH2-. The preferred one is -CH2-, -〇-, and the above-mentioned R11, R12, r13, and R|4 5 are not particularly limited, and R, 6, Ri, and RI8 are appropriately selected, and examples thereof include carbon. The number may be an alkenyl group, -OR, only ι9 <alkyl group, a carbon number of 1 to 20 (quasi-R is not a monovalent organic group), a soil, an arylamine group, a diarylamine group or the like. Earth and square oxygen The above-mentioned tooth atom ′ is, for example, fluorine or chlorine. From the viewpoint of analytical properties, the above-mentioned RU and Ri23. Preferably, it is a hydrogen atom, a carbon number of 1 to 2 Torr, a derivative of -0Ri9, and *Rl4, and an aromatic group represented by the general formula (VI): a diatomic atom. There is a particular limitation, and a ratio of 20% to 20% by mass, more preferably 20% by mass to 70% by mass, and preferably 20% of the structural unit represented by the formula (V) can be used according to the purpose. Second, the above-mentioned mass composition ratio means that 乂 is contained in the aromatic group = aromatic group, and the diisocyanate duck represented by the above formula (7): ratio is not limited, and can be appropriately selected according to the purpose. The system is free of diisocyanate, 2, toluene diisocyanate dimer: Ή stupid - monoisocyanate, ρ- benzene dimethyl diisoxamic acid slightly methyl bis-acid Ester, 4,4,-diphenylmethane diisocyanate (10) fluorenyl diiso ==,?,3'-dimercaptobiphenyl_4,4, diisocyanine '2", murine I 曰 compound,曱 曱 二 二 二 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 : atmosphere: =..., bis(cyclohexyliso-acidic acid), methylcyclohexane, 2,4 (;,)-isoisocyanuric acid A_H ^ ^,3-(兵虱鲛s曰Alicyclic cyanoquinone esters such as methyl)cyclohexane ;丨3_butanediol, xt „ machi 1 Wudou and toluene diisochlorinated brewing West 2 2 molar addition 虱酉 owe. ^ Do not know the reaction with the isocyanate _ isocyanic acid Compounds, etc. These types can be used in two or more types. These are hard to be used in the early stage, and can be used together. From the viewpoint of hardness, the compound of the diisocyanate S is particularly good. , /香^ ψ A &amp; . 〒本-isocyanate, m_ (MDI) 〇 甲 说 说 说 异 异 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又The diisocyanate compound represented by the general formula (V) and the triiso(4) S compound and the ethylenic unsaturated monofunctional amine compound are added in an equivalent amount of 1 equivalent of the cyanide compound, which is not particularly limited. The compound described in the paragraph [0034Ί~[0035], such as the one reported in Japanese Patent Laid-Open No. 2005-250438, is exemplified by the following. The monofunctional alcohol of the ethylenically unsaturated group or the aforementioned monofunctional σ ′′′ is also limited, and may be appropriately selected according to the purpose. For example, a paragraph of the publication of the Japanese Patent Publication No. 2〇〇5·25〇438 (Ο.)]~ [0040] a compound that is redundant, etc. _ at the end of the primary bond, and having a polyunsaturated group A method for producing an ethylene phthalate resin having a small number of carboxyl groups in the amine group and having a vinyl phthalate resin in the side chain _24-201209066 The method for producing the polyurethane resin is not particularly limited, and may be appropriately selected according to the purpose. For example, the above-mentioned diisocyanate compound, the above diol compound, the above carboxylic acid compound, and optionally other copolymerization components are added to an aprotic solvent, and a known catalyst according to the reactivity of each reactivity is added and heated. , by means of synthesis, etc. The molar ratio (Ma:Mb) of the diisocyanate and the diol compound used for the synthesis is not particularly limited and may be appropriately selected according to the purpose, preferably 1:1 to 1.2 μm, by using an alcohol or an amine. When the treatment is carried out, a product of a desired physical property such as molecular enthalpy or viscosity is synthesized in such a manner that no isocyanic acid remains in the final form. The weight of the polyamine phthalate resin as the alkali-developable resin

Average molecular weight" The acid value of the aforementioned alkali-developable resin

Do not limit, according to g~12〇mgK〇H/g, -25- 201209066, preferably 30mgKOH/g~ll〇mgK〇H/g, especially good 3 51^1&lt;:011/§~1〇〇 11^1&lt;:011/8. If the acid value is less than 2〇111§1 (:〇11/§, the developability will become insufficient, and if it exceeds 12〇mgK〇H/g, then the development speed will become too high and the development control will become The acid value can be measured, for example, according to JIS K0070. However, when the sample is not dissolved, dioxane or tetrahydrofuran or the like is used as a solvent. The alkali-developable resin is in the solid content of the photosensitive composition. The amount of the film is preferably from 5% by mass to 80% by mass, more preferably from 3% by mass to 6% by mass, and more than 5% by mass. If the content is more than 5% by mass, the developability and the exposure sensitivity are good. When the amount is 80% by mass or less, the adhesion of the photosensitive layer can be prevented from becoming too strong. &lt;Polymerizable compound&gt; The 'polymerizable compound is not particularly limited, and can be appropriately selected according to the purpose. Examples of the functional group having an ethylenically unsaturated group. Examples of the functional group having an ethylenically unsaturated group include an ene group, a methacryl group, an acrylamide group, and a methyl propylene group. :, vinyl phenyl, vinyl ester, vinyl ether And an allyl group, an allyl ester group, etc. The compound having i or more ethylenically unsaturated groups is not particularly limited, and may be appropriately selected according to the purpose, and may be appropriately exemplified by The sulfhydryl-based monomer is not particularly limited, and may be appropriately selected according to the purpose, and examples thereof include polyethylene glycol mono Base) -26- 201209066 Acrylate, polypropylene glycol mono (methyl) dienoic acid, phenoxy

Internal acid cool, stupid oxyethyl (formate or monofunctional methacrylic acid, polypropylene glycol di(methyl) propyl) acrylate, trimethyl propyl triacrylate, three armor Base alcohol-(meth)acrylic acid vinegar, neopentaerythritol tris(tri) methacrylate, di-new L ester, dipentaerythritol penta (meth) acrylate, hexane diol II (Meth) acrylate, trimethylolpropane tris(propylene octyloxypropyl), tris(propylene decyloxyethyl) 1,3-decyl isocyanate, bis(propylene decyloxy) Ethyl) cyanurate, glycerol tri(meth) acrylate; trihydromethane propane, glycerol, bisphenol, etc. in polyfunctional alcohols to make ethylene oxide or propylene oxide After the reaction, (mercapto) acrylate is used, and a polyfunctional acrylate or methacrylate such as an epoxy acrylate of a reaction product of an epoxy resin and (meth)acrylic acid is obtained. Among these, 'excellent is trimethylolpropane tris(mercapto) acrylate, neopentyl alcohol tetra(meth) acrylate, dipentaerythritol hexa(meth) acrylate, dipentaerythritol Alcohol penta(indenyl) acrylate, dicyclopentane dimethylol di(indenyl) acrylate vinegar. The content of the polymerizable compound in the solid content of the photosensitive composition is preferably from 5% by mass to 50% by mass, more preferably from 1% by mass to 40% by mass. When the content is 5% by mass or more, the developability and the exposure sensitivity are good, and when it is 50% by mass or less, the adhesion of the photosensitive layer can be prevented from becoming too strong. &lt;Photopolymerization initiator&gt; -27-201209066 With respect to the above-mentioned light, as long as it has the ability to initiate polymerization of the above-mentioned Chinese compound, it is preferable to select the combination of μ and t, for example, preferably ultraviolet rays. Scope: = For those who have the purpose of being photosensitive, it may be an active agent which generates active radicals by photoexcitation and enhances the light, and generates an initiator which acts as a cationic polymerization. Further, it is also preferred that the photopolymerization initiator has a composition having at least about the number of wavelengths in a range of at least about 300 nm to 800 nm. The above wavelength is more preferably a photon absorption system ^ 1 main horse 33 〇 nm to 500 nm 〇 The photopolymerization initiator is preferably neutral. Other photopolymerization initiators may be contained as needed. . Agent. In addition, as for the aforementioned neutral photopolymerization initiator, You Zhaozheng recognizes A / / has special restrictions,

According to the purpose of ‘,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, , (double) sulfhydryl phosphine or diphenyl ketone-based eight, wrinkle #, let G-based compounds, compounds, 9 栌 栌 ether compounds, ketal derivatives 9 ^ hawthorn compounds for more Two or more types may be used in combination. &lt; τ丨王九聚σ initiator For the above photopolymerization, add 丨丨, π with mountains, phosphine or 7 . &quot; For example, (double) sulfhydryl oxidized Λ Λ 酉曰頬, phenylethyl _ _ _ Λ 醚 ether etherification / / base _ series compounds, benzene, ... The compound, 9·oxysulfuric acid is sensitized: 1 ng organic peracid, sulfur compound, and the like. Among these, the use of beauty &amp; S sense, preservative, and photosensitive layer and printed wiring board to form a base phosphine oxide red ... § and 5, Quan Jia is a bismuth derivative, (double) sputum, S ”: t , an ethyl ketone compound, a diphenyl ketone compound, an ether compound, a ketal derivative compound, a 9-oxosulfanthene -28-201209066, a bis(indenyl)phosphine oxide, the aforementioned benzene The s-synthesis compound, the above-mentioned monophenyl-based homologous compound, the above-mentioned benzoin ether-based compound, the ketal-heterobiological compound, and the above-mentioned oxonium sulfonium compound may be exemplified by Japanese Unexamined Patent Publication No. 2010-256399 (d) fluorenylphosphine oxide acetophenone-based compound, diphenyl ketone-based compound, benzoin _ i human 'heart compound, ketal derivative compound, paragraph (〇〇42) Hawthorn compound, etc. Milk sulphur In the case of the aforementioned hydrazine derivative, it can be 20 1 0-256399, such as a paragraph that does not open a paragraph [〇〇43] ~ 肟 derivative, etc. L 〇 5 9] The above-mentioned photopolymerization initiators contained in δ are more than one species. Shu polymerization initiator than &amp; today, +, #, Bu is not content-based solids content Laid% pF months a i "of the composition is good. "Quality: I:,, buy summer%, live better. Specially good for 0.5 mass 〇 / ] ‘ · Quality % ~ 20 mass 〇 / 〇, only 罝 / 〇 ~ 1 5 quality 〇 / 〇. &lt;Hot cross-linking agent&gt; Talk about hot-parent agent, you, Λ古〇 | W goods... There are special restrictions, should choose, for the improvement of 4 umbrellas + according to the purpose of the appropriate 4 nine layers in the hardening In the range of adverse effects, such as the field strength, in the case of no development (for example, in one molecule, ε, for example, at least 2 ring epoxy compounds, for example, epoxy compound 1J), too, milk, milk An oxirane group having an ox丨, (oxetanyl) group of epoxy v 2 propylene oxide oxypropylene compounds in one molecule, as described in the publication of the publication, and an ancient IS-opening 2007-47729 The position of the oxyethyl group has an alkyl group, the outer ring thereof, the milk-based compound, the compound of the β-Rich base, the propylene cyanide -29-201209066 alkylation port, the polyisocyanate compound, A compound (blocked polyisocyanate compound), an oxazoline derivative or the like obtained by reacting a polyisocyanate or a derivative thereof with an isocyanate group and a blocking agent. &gt; One &quot; A melamine derivative can be used as the aforementioned thermal crosslinking agent. The melamine derivative may, for example, be methylol melamine', alkylated ruthenium melamine (a compound obtained by hydrazine methylol &amp; butyl, etc.). These systems are used alone or in combination of two or more. Among these, it is based on the point that the storage stability is good and the surface hardness of the photosensitive layer or the film strength of the cured film itself is effectively improved. The methylol melamine is preferably a hexamethylated hydroxymethyl melamine. The epoxy group compound may, for example, be an epoxy compound having at least two oxirane groups in the oxime molecule. The epoxy group compound having at least two epoxy groups having an alkyl group at the β position in the molecule, and the epoxy group having at least two ethylene oxide groups in one molecule, may be mentioned. For example, bisphenol F type epoxy resin (Epotohto YDF-HO, manufactured by Tohto Kasei Co., Ltd.), ruthenium phenol type or biphenol type epoxy resin ("YX4000, manufactured by Nippon Epoxy Co., Ltd.") or the like a mixture, a heterocyclic epoxy resin having a trimeric isocyanate skeleton ("TEPIC, manufactured by Nissan Chemical Industry Co., Ltd.", "Osaka 犷, PT8 1 Ο, Ciba · Specialty · Chemicals §1 _ 堃,

J clothing "seeking", double A type epoxy resin, novolak type epoxy resin, bisphenol F type epoxy tree ^, water added bisphenol A type epoxy resin, bisphenol s type epoxy resin, - clothing Rolled tree sap, phenol novolac type epoxy resin, nonylphenol novolac type epoxy resin, etched epoxy resin (such as low brominated epoxy resin, high-functional epoxy resin, - 戍1匕本• 30-201209066 jun varnish type epoxy resin, etc.), bisphenol condensed epoxy epoxide ("VG-3 101; made by printec"), acryl-containing double-anti-type A epoxy resin, ginseng Phenol methane type epoxy resin, diphenoyl bisphenol type epoxy resin, phenol extended biphenyl type epoxy resin, and dipentyl pentadiene type epoxy resin ("HP-7200, HP-7200H; Greater Japan" Manufactured by Huaguo Chemical Industry Co., Ltd., epoxy propylamine type epoxy resin (_aminodiphenyl decane type epoxy resin, diepoxypropyl aniline, = - oxalic propyl phenol, etc.), Glycidyl ester type epoxy resin (citric acid diacetal vinegar, diepoxypropyl adipate, hexahydrophthalic acid diepoxypropyl brewing, _ poly 1-% oxypropyl S, etc.), carbendazim type epoxy resin, alicyclic jade oxygen resin (3,4-epoxycyclohexyldecyl-3,4,-epoxy ring Tian &amp; ^ T 1^ vinegar, bis(3,4·epoxycyclohexylmethyl) adipate, dicyclopentadienyl epoxide, GT-300, GT-400, ZEHPE 3150; Silent Chemical Industry Co., Ltd., etc.) 醯imine-type alicyclic epoxy resin, trishydroxyphenylmethane epoxy resin, bisphenol A novolak-type oxygen resin, tetrahydroxyphenylethane Epoxy resin, epoxy propyl citrate, sulphuric acid, tetradecyl propyl diphenyl phenyl hydrazine, epoxy resin, naphthyl aralkyl epoxy resin, naphthol phenolic aldehyde A varnish type epoxy resin and a 4-functional naphthalene type epoxy resin are commercially available as r ESN_i90, ESN-360; manufactured by Nippon Steel Chemical Co., Ltd., "HP-4032, EXA-4750, EXA-4700; Ink Chemical Industry Co., Ltd., etc., by the addition reaction of a phenolic compound with divinylbenzene or a cyclopentadienyl dilute compound to obtain a compound and a gas An alcohol reactant, an epoxy group obtained by epoxidizing a ring-opening polymer of 4-vinylcyclohexene-1-oxide with peracetic acid or the like, and having a linear -31-201209066 phosphorus-containing structure epoxy resin Epoxy resin having a ring-shaped phosphorus structure, α. methyl stilbene type liquid crystal epoxy resin, diphenylmethyl sulfonyl benzene type liquid a 曰 epoxy resin, azo phenyl type liquid crystal epoxy resin , azo decyl phenyl liquid crystal epoxy resin, binaphthyl liquid crystal epoxy resin, fluorene epoxy resin, epoxy propyl methacrylate copolymer epoxy resin ("CP-50S, CP-50M; manufactured by Nippon Oil & Fat Co., Ltd.), copolymerized epoxy resin of cyclohexylmaleimide and epoxypropyl methacrylate, bis(epoxypropyloxyphenyl)fluorene type Epoxy resin, bis(epoxypropyloxyphenyl) adamantane type epoxy resin, and the like. These may be used alone or in combination of two or more. Further, in addition to the above epoxy group having at least two ethylene oxide groups in one molecule, an epoxy compound having at least one molecule having an epoxy group having an alkyl group at the β position may be used. Particularly preferred is a compound having an epoxy group substituted with an alkyl group at the p-position (more specifically, a β-alkyl-substituted epoxypropyl group, etc.). The epoxy group compound having at least an epoxy group having an alkyl group at the β-position may be one or more epoxy groups contained in one molecule, all of which are ρ-alkyl-substituted epoxy propyl groups, or may be at least one The epoxy group is an alkyl-substituted epoxypropyl group. For example, the propylene oxide compound described in paragraph [0074] of JP-A-2010-256399 can be mentioned. The polyisocyanate compound and the like described in paragraph [0075] of JP-A-20 10-256399, for example, are mentioned. -32-201209066 The above-mentioned blocked polyisocyanate compound may, for example, be a compound described in 曰本特开2 (paragraph [10%%] of H0_256399]. For example, hydrazine, 3-bisazino-2-indenyl benzene, M-bis (4m octagonal bis(2-oxazoline), etc. + _ about the aforementioned melamine derivative' may be mentioned, for example In the paragraph of 〇10-256399, the 〇f special creature, etc. "W. The dimeric amide derivative carried by the above-mentioned thermal crosslinking agent is not particularly limited in the above-mentioned photosensitive group, and can be used according to the purpose: 3 1% by mass to 50 皙田., 乂 且 且 选择 , , , 较佳 较佳 选择 选择 选择 选择 选择 选择 选择 选择 前述 5 5 5 5 5 5 5 5 更 更 更 更 更 更 更 / / / / / / / / / / / Quality. / Below the target. 'The film strength of the cured film is improved &lt;;;;;; I, Jl — — = = = : The language is not particularly limited, and may be, for example, a diluent, ^ y agent, thermal polymerization inhibitor, 1 β filling, thermal hardening promotion, etc., can also enter two or two plasticizers, colorants (coloring pigments or dyes: agents (for example)胄 性 + adhesion promoter to the surface of the substrate and other leveling agents, peeling accelerator,: V4 filler, defoamer, flame retardant, chain transfer agent, etc.) Several emulsifiers, fragrances, surface tension The modifier, the stability of the film containing the components, and the properties of the photosensitive-diluent (solvent)/membrane property of the target are adjusted. -33- 201209066 There is no speciality with respect to the aforementioned diluent. The restriction can be appropriately selected according to the purpose, and examples thereof include alcohols such as decyl alcohol, ethanol, n-propanol, isopropanol, n-butanol, secondary butanol, and n-hexanol; acetone, mercaptoethyl ketone, Ketones such as mercaptoisobutyl ketone, cyclohexanone, diisobutyl ketone; ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, ethyl propionate, dimethyl decanoate, benzoin Ester of ethyl acetate, methoxypropyl acetate, etc.; aromatic hydrocarbons such as toluene, diphenylbenzene, benzene, ethylbenzene; tetracarbonized carbon, triethylene glycol, chloroform, 1,1 , 1-trimethylethane, dioxane, mono-benzene, etc.; tetrahydrofuran, diethyl ether, ethylene glycol An ether such as mercaptoether, ethylene glycol monoethyl ether or 1-decyloxy-2-propanol; dinonylguanamine, dimercaptoacetamide, dimercaptosulfoxide, sulfolane and the like. These may be used singly or in combination of two or more. A known surfactant may be added. The content of the diluent in the photosensitive composition is preferably 0.5% by mass to 60% by mass. More preferably, it is 5% by mass to 50% by mass. The above-mentioned filler is described in detail in paragraphs [0098] to [0099] of JP-A-2008-250074, for example. Sections [0101] to [0102] of the publication No. 2008-250074. The above-mentioned thermosetting accelerator is described in detail in, for example, paragraph [0093] of JP-A-2008-250074. The above-mentioned plasticizer is described in detail in, for example, paragraphs [0103] to [0104] of JP-A-2008-250074. The coloring agent is described in detail in, for example, paragraphs [0105] to [0106] of JP-A-2008-250074. -34-201209066 The above-mentioned adhesion promoter is described in detail in, for example, paragraphs [〇1〇7] to [〇1〇9] of Japanese Patent Laid-Open No. 20 0 8-25 0074. (Photosensitive film) The photosensitive film of the present invention comprises at least a support layer and a photosensitive layer comprising the photosensitive composition of the present invention on the support, and further has other layers as needed. - Support - The support system is not particularly limited and may be appropriately selected according to the purpose, but it is preferable that the surface layer is preferably peeled off and the light transmittance is good, and the surface smoothness is better. The support is preferably made of a synthetic resin and is transparent, and examples thereof include polyacetic acid ethane vinegar, polyethylene naphthalate, polypropylene, polyethylene triacetate, cellulose diacetate, Poly(methyl) acrylate, poly(meth)acrylic copolymer, polyvinyl chloride, polyethylene, polycarbonate, polystyrene, celluloid

Various kinds of substances, polyamines, polyimine, A 7u ^ K gas ethylene · S phthalate copolymer, polyethylene phthalate, cellulose film, and thin film. This #system彳__ above. Among them, the special thickness is the combination of the two types of the support, and the thickness of the support is not particularly suitable, for example, J J is used, the purpose is added -100, and the best is 8_50 (four). _~150 call, more preferably for the purpose of the aforementioned support body, the length is not particularly limited. The shape is not particularly limited, and may be, for example, a long strip-shaped branch system of a long strip shape, for example, a length of from 10 m to 20,000 m - 35 - 201209066 - a photosensitive layer - the above-mentioned photosensitive, and the limitation may be Further, the above-mentioned purpose is suitably applied to the above-mentioned emulsified or distributed solution, and the above-mentioned sensation can be made according to the same thing as the objective agent. The coating may be appropriately selected, and the machine or the roll coating support may be directly dried or the like for a different second to 15 minutes, and the above-mentioned feeling may be suitably 2 μηι to 5 0 μηη, 4 &lt;other layers&gt; Suitably, as long as it is a layer containing a photosensitive composition, it is suitably selected without a special purpose. The number of layers of the photosensitive layer is not particularly limited, and may be, for example, one layer or two or more layers. The method of forming the photosensitive layer is a method in which the photosensitive composition is dissolved in water or a solvent to prepare a photosensitive composition solution, and is directly coated and dried to deposit a layer. The solvent of the optical composition solution is not particularly limited, and may be appropriately selected, for example, the method of dilution with the above-mentioned dilution is not particularly limited, and examples thereof include a spin coater, a slit spin coater, and a mold. A coating machine, a curtain coater, or the like, in the above coating method. The conditions are based on the composition of the solvent, the use ratio is 60C ~ 11 〇. The thickness of the light layer is not particularly limited, and may be, for example, preferably 1 μηι 1 to 1 μm, more preferably 4 μπι to 30 μπι. The layer is not particularly limited, and may be, for example, a protective thin layer, a thermoplastic resin layer, a -36-201209066 shielding layer, a peeling layer, an adhesive layer, a light absorbing layer, a surface protective layer or the like. The photosensitive film may have one or more of these layers, or may have two or more types. &lt;&lt;Protective Film&gt;&gt; The photosensitive film may also form a protective film on the photosensitive layer. The protective film may, for example, be used in the above-mentioned support, paper, laminated polyethylene, or polypropylene. Among these, a polyethylene film or a polypropylene film is preferable. The thickness of the protective film is not particularly limited and may be appropriately selected according to the purpose, and is, for example, preferably 5 μm to 1 0 0 μm, more preferably 8 μm to 50 μm, and particularly preferably ΙΟμηι to 30 μm. The combination of the support and the protective film (support/protective film) may, for example, be polyethylene terephthalate/polypropylene, polyethylene terephthalate/polyethylene, polyethylene/cels. , polyimine / polypropylene, polyethylene terephthalate / polyethylene terephthalate and the like. Further, by performing surface treatment on at least one of the support and the protective film, the interlayer adhesion can be adjusted. The surface treatment of the support may be performed to increase the adhesion to the photosensitive layer, and examples thereof include coating of an undercoat layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high-frequency irradiation treatment, and glow discharge. Irradiation treatment, active plasma irradiation treatment, laser irradiation treatment, and the like. Further, the static friction coefficient of the support and the protective film is preferably from 0.3 to 1.4, more preferably from 0.5 to 1.2. -37- 0·3 is uneven, and it is possible to prevent the cause of being 1/4 or less. 201209066 The above-mentioned static friction coefficient is curled into a good roll shape when it is formed into a roll shape.感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光 感光The long strip photosensitive thin port system has special restrictions, which can be selected by you, for example, a range of 10m to 20,000m. Alternatively, it can be semi-processed into a ''will be used by the 6 1 user. L〇〇m~1 〇〇〇m dip shovel m ι'υυυηι The length of the strip is made into a roll shape. In this case, the father is rolled up so that the support body becomes the same as the night. The light-sensitive photosensitive film is cut into a sheet shape, and it is preferable to provide a separator (especially a moisture-proof person or a desiccant) from the viewpoint of protecting the end face and preventing edge fusion. A good moisture permeability material is also used for the package. The protective film may be surface-treated in order to adjust the protective film and the photosensitive layer. The surface treatment is to form a polyorganoquinone on the surface of the protective film. An undercoat layer of a polymer such as oxyalkylene, fluorinated fe, polyvinyl fluoride or polyvinyl alcohol. The formation may be carried out by applying the polymer coating liquid to the surface of the film, and drying at 30 ° C to 15 ° C for 1 minute to 30 minutes, and the temperature at the time of drying is particularly preferably 50 〇 c 12 (Tc. Photosensitive layered product) The photosensitive layered system has at least a base and a photosensitive layer provided thereon, and the other layer which is appropriately selected as needed is laminated, and the photosensitive layer is the above-mentioned photosensitive film transferer produced by the above-described production method. 'The same structure as above. The sliding guide can be rolled, the length of which is sheared and the side is. When it is at the end, the front is as thin as the base of the polyene. The base is formed. Photo-38- 201209066 &lt;Substrate&gt; The substrate to be processed formed by the photosensitive layer of the base system or the transfer target to which at least the photosensitive layer of the photosensitive film of the present invention is transferred is not particularly limited, and may be appropriately selected depending on the purpose, for example It can be arbitrarily selected from those having a high surface smoothness to those having a surface unevenness. It is preferable to use a so-called substrate for the plate-shaped substrate. Specifically, a substrate for manufacturing a printed wiring board is known (printed) (a substrate), a glass plate (such as a soda glass plate), a synthetic resin film, a paper, a metal plate, etc. <Method for Producing Photosensitive Laminate> The method for producing the photosensitive layered body may be a side A method of transferring at least one of heat and pressure of at least one of the photosensitive layers of the photosensitive film of the present invention. The method for producing a photosensitive laminate is to expose the photosensitive property of the present invention to the surface of the substrate. In the case where the photosensitive film has the protective film, at least the film is heated and pressurized, and the protective film is preferably peeled off, and the heating temperature is superimposed on the substrate. It is not particularly limited and may be appropriately selected depending on the purpose, and is preferably, for example, 15. (: 〜18 (TC, more preferably 6 (rc~i4〇t.) The pressurized pressure is not particularly limited and may be appropriately selected according to the purpose, and is preferably, for example, O.iMPH 〇Mpa, 〇.2MPa~〇 .8MPa. The two 仃 既 仃 仃 仃 叩 I :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: :: Nichlg0-Mort〇n Co., Ltd., νρΐ3〇). -39- 201209066 The photosensitive film of the present invention and the photosensitive laminate have a uniform film thickness and a low incidence of surface defects such as pinholes or depressions. - The corpse 7 can efficiently form a permanent pattern with excellent insulation and high definition (a smear film, an interlayer insulating film, a photoresist pattern, etc.). Therefore, it can be widely used as a high-definition permanent pattern in the field of electronic materials. In particular, it can be used for permanent pattern formation of printed substrates. '(Permanent pattern forming method) The permanent pattern forming method of the present invention contains at least an exposure step, and further, if necessary, a step of developing a suitable selection step or the like. &lt;Exposure Step&gt;: The exposure step is a step of exposing the photosensitive layer in the photosensitive laminate of the present invention. Regarding the photosensitive laminate system of the present invention, the target of the exposure is as described above, σ II Elephant/, the anatomical layer of the photosensitive laminate t is not limited by the county brothers, and the car father can be appropriately selected according to the purpose, for example, for the above ήί*, +, + X, , .. ,. In the laminated body, the laminated body is formed by laminating a photosensitive film into the oyster 2 on the material. At least one of heating and pressing, and the exposure system of the soil is not particularly selected. Exposure, analog exposure, can be adapted according to the purpose. <Other steps> The above other steps are not preferred, and may be, for example, other limitations of the substrate, which may be subjected to a hardening treatment step and a post exposure step 2 according to the purpose. ★ Surface treatment step, development step, &lt;&lt;Development step&gt;&gt;, etc. 6 '40-201209066 For the development described above, the above-mentioned development is carried out. The method of removing the unhardened region is not exposed to the stomach. System For the purpose of selecting the above-mentioned developer, it is not particularly preferable to select, for example, an alkaline water q can be used in accordance with an organic solvent, etc. +, preferably weakly inferior = the alkali component of the developing aqueous solution may, for example, be a hydrogen sulphate. Kunming L-ring, hydrogen-negative potassium sulphate, lithium carbonate, sodium carbonate, carbonic acid fly-rolling-- The pH of the weakly alkaline aqueous solution is preferably 8 to 12, 9~, for example, the pH of the weakly alkaline aqueous solution is preferably arbitrarily determined by lithium hydride, potassium strontium carbonate, sodium phosphate, phosphoric acid, sodium pyrophosphate, and tar. 1 1. The weakly alkaline aqueous solution may, for example, be a sodium sulphate water bath or a potassium carbonate aqueous solution of ruthenium or the like. The temperature of the developer may be suitably selected in accordance with development of the photosensitive layer, for example, &apos; preferably about 25. (:~4 (TC. For example, the surfactant solution can also be used in combination with a surfactant, an antifoaming agent, (for example, ethylene diamine, ethanolamine, tetraammonium hydroxide, diamethylene ethoxide, morpholine, Triethanolamine or the like), or used to promote a display solvent (for example, alcohols, ketones, esters, ethers, guanamines, etc.), etc. Further, the aforementioned developer may be a water system of a mixed water or an aqueous alkali solvent. The developer may be a separate organic solvent. &lt;&lt;hardening treatment step&gt;&gt; The hardening treatment step is a step of hardening the photosensitive layer in the pattern formed by the development step described above. Shadow liquid to the purpose of adding liquid, there is the weak test, hydrogen hydride, potassium, boron, the best amount of ~ 5 sexual force to organic diamine, shadow, internal and organic, on -41- 201209066 As far as the above-mentioned hardening treatment steps are concerned, there is no special 丨Rp J suction, which can be appropriately selected according to the line of the illuminating case, and can be appropriately selected, for example, full exposure. Treatment, full heat treatment, etc. The blanket exposure treatment method, for example, a single patient may be in the

The method of forming a full-line exposure of the aforementioned layer _ L w with the permanent pattern described above. By this overall exposure, it is possible to promote the hardening of the resin in the photosensitive composition which hardly forms the above-mentioned photosensitive layer, and to harden the surface of the water-repellent pattern of new, +, a κ. There is no special method for performing the above-mentioned comprehensive exposure, and it can be appropriately selected according to the purpose, and can be suitably used, for example, for the υν exposure machine of the 轺古阿 &amp; A pressure mercury lamp. It is preferable to reduce the total heating of the layered body on which the permanent pattern is formed after the development of the above. By this overall heating, the film strength of the aforementioned water-repellent pattern surface can be improved. The heating temperature for the above overall heating is preferably 120 t: ~: &gt; ςη. ~ Ό 〇 C, more 1 20 ° C ~ 20 0 ° C. If the heating temperature is 1 2 〇〇 c in μ Å, the strength of the lift film can be heated to be 250. (The following, Βι| prevents decomposition of the resin in the front photosensitive composition, prevents the film from being clear, and the shell is fragile. The heating time of the above-mentioned overall heating is preferably from 15 minutes to 60 minutes. 〇min~1 2 0 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 In the method of forming a permanent pattern forming at least one of a protective ruthenium, an interlayer insulating film, and a solder resist pattern, a permanent pattern can be formed on the printed wiring board by the permanent pattern forming method, and further, Soldering is performed. The metal layer is exposed on the surface of the printed wiring board by forming the hardened layer of the permanent pattern by the development. The metal layer exposed on the surface of the printed wiring board is plated with gold and then soldered; A semiconductor, a member, etc. are placed on the soldered portion. At this time, the permanent pattern of the hardened layer functions as a permanent pattern. In order to protect the film or the insulating film (interlayer insulating film) and the function of the solder resist, it is possible to prevent an external impact or an adjacent electrode from being electrically connected. (Printed substrate) The printed substrate of the present invention has at least a base and is permanently The permanent pattern formed by the pattern forming method is formed into another member which is appropriately selected. 〃 Other members are not particularly limited and may be appropriately selected according to the purpose, and for example, further between the substrate and the permanent pattern may be mentioned. A layered (buUd_up) substrate or the like provided with an insulating layer. [Examples] - The present invention is described below with reference to the examples of the present invention, but the present invention is not limited thereto. The acid value and the weight average molecular weight are measured according to the following method: &lt;Acid value&gt; The measurement is carried out. However, the sample has no sulphur as a solvent. When the acid value is dissolved according to the JIS K0070 method, dioxane or tetra is used. Hydrogen fur-43-201209066 &lt;Weight average molecular weight&gt; The weight average molecular weight described above was measured using a high-speed GPC apparatus (manufactured by Toyo Soda Co., Ltd., HLC-802A). That is, a 6% by mass solution of THF (tetrahydrofuran) was used as a sample solution, and two TSKgelGMH6 were used for the column, and a sample of 200 Å was injected, and the solution was dissolved in the THF solution, and the refractive index detector was used at 25 ° C. The weight average molecular weight was determined from the molecular weight distribution curve corrected by standard polystyrene. (Synthesis Example 1) - Synthesis of polyamine phthalic acid vinegar resin U-1 _ 5 〇 with condenser and stirrer In a 〇mL 3-neck round bottom flask, 1.62 g (0. 〇18 mol) lactic acid, 8 〇〇g (〇〇54 mol) 2 2 bis(hydroxymethyl)butyric acid (7)^^(4) and 15.38 g (〇〇96 mol) glycerol mono- acrylate was dissolved in 73 g of cyclohexanone. Add 30.03g ((M2 #耳) 4,4,· diphenylmethane diisocyanate from the purpose (face), 4.80g (0_03 mole) l, 4-phenylene diisocyanate (pDI), 〇ig 2,6-di-butyl hydroxytoluene, and ruthenium 2g as a catalyst. Trade name: NE〇STANNU_600 (made by Nitto Chemical Co., Ltd.), in Nai. Then, it was diluted with methyl alcohol 906 and allowed to stand for 30 minutes to obtain a solution of a polyurethane urethane resin U-1 represented by the following formula (solid content: 45 mass%). The solid content of the acid ester resin U-1 solution is 68mgeK〇H/g. The weight average measured by gel permeation chromatography (GPC) is 8.5 Å (the standard of polyethylene). &lt;Polyurethane resin U -1 &gt; -44 - 201209066

However, in the above formula, al, bl, cl, dl, and el represent the composition ratio (% by mass). (Synthesis Example 2) - Synthesis of Polyaminophthalate Resin U-2 - Except that in Synthesis Example 1, mont lactic acid, 8.00 g (0.054 mol) of 2,2-bis(hydroxy fluorenyl) Butyric acid (DMBA) and 15_38 g (0.096 mol) of glycerol monomethacrylate were changed to 2.41 g (0.018 mol) of malic acid, 5 23 g (〇〇39 mol) of 2 2 bis(hydroxymethyl)propionic acid ( DMPA) and 17.78g (〇.in mole) glycerol monodecyl acrylate S, 7 3 g of cyclohexanone was changed to 7 4 g, 30.03g (0.12 mole) 4,4' - Diphenyldecane diisocyanate (MDI) with 4.80 g (0.03 mol) of ι,4-phenylene diisocyanate (PDIy^ more 30.03 g (0.12 mol) 4,4,-diphenylnonane II The isocyanate (MDI) was synthesized in the same manner as in Synthesis Example 1 except that 5.05 g (0.03 mol) of hexamethylene diisocyanate (HMm) was used, and a polyamine phthalate resin U-2 solution represented by the following formula was synthesized (solid The content of the solid content of the polyamino phthalate resin U-2 solution is 64 mgKOH/g'. Styrene standard) is 6,500. <Polyamine phthalic acid Resin U-2 &gt;

A2

-45-201209066 However, in the above formula, a2, b2, c2, d2 and e2 represent the composition ratio (% by mass). (Synthesis Example 3) - Polyurethane resin U-3 synthesis - except in Synthesis Example 1, '1·62 § (0·018 mol) lactic acid, 8.00 g (0.054 mol) 2, 2 - bis(hydroxyindenyl)butyric acid (DMBA) and 15.38 g (0.096 mol) of glycerol monomethacrylate were changed to 2.6 8 g (0.020 mol) of malic acid, 3.46 g (〇.〇23 mol) 2, 2-bis(hydroxyindenyl)butyric acid (DMBA) with 22.96 g (0.143 mol) of glycerol monomethacrylate, 73 g of cyclohexanone was changed to 78 g, and 30.03 g (0.12 mol) of 4,4' -Diphenyldecane diisocyanate (MDI) and 4.80 g (0. 3 mol) 1,4-extended diisocyanate (PDI) were changed to 35.05 g (0.167 mol) trimethylhexamethylene The polyaminophthalate resin U-3 solution (solid content: 45 mass%) represented by the following formula was synthesized in the same manner as in Synthesis Example 1 except for the diisocyanate (TMHDI). The solid content of the obtained polyurethane resin U-3 solution was 5 2 mgKOH/g', and the weight average molecular weight (polystyrene standard) measured by gel permeation chromatography (Gpc) was 7, 〇 Hey. &lt;Polyurethane resin U - 3 &gt;

0丄OH c3

Τί 4〇ίh3 L Ο

OH OH only in the above formula, b3, c3, d3 and h3 represent the composition ratio (% by mass) 0 -46- 201209066 (Synthesis Example 4) - Synthesis of polyamino phthalate resin U-4 - except in synthesis In Example 1, 1.62 g (0.018 mol) of lactic acid, 8.00 g (0.054 mol) of 2,2-bis(methylidene)butyric acid (DMBA) and 15.3 8 g (0.096 mol) of glycerol monothiol were used. The acrylate was changed to 3 lg (〇〇2 mol) by hexanoic acid, 11.2 g (〇.〇8 mol) 2,2-bis(hydroxymethyl)propionic acid (DMPA), 23 g (0.14 mol) of glycerol Monomethacrylate with 4.7g (0.01 mole) polypropylene glycol (ppGi〇〇〇), 73g of cyclohexanone changed to 6〇g, 30.03g (0.12 mole) 4,4, _diphenyl Methane diisocyanate (MDI) was changed to 4.80 g (0_〇3 mol}1,4-phenylene diisocyanate (1&gt;1) 1) to 58 g (0.23 mol) of 4,4,-diphenylfluorene. In the same manner as in Synthesis Example 1, except for the alkyl diisocyanate (mdi), a polyurethane resin U-4 solution (solid content: 45 mass%) represented by the following formula was synthesized. The polyamine-based brewing of the two fci surnames ± &amp; § the fat content of the U-4 solution is 58 mg KOH / g, measured by gel thinning & ◊ ◊ 层析 (GPC) The weight average molecular weight (polystyrene standard 1 5 not +) is 9, 〇〇〇. &lt;polyamino phthalate resin u_4&gt;

, ΟΗ, the ratio (% by mass) in the above formula. (Synthesis Example 5) -47-201209066 - Synthesis of polyamino phthalate resin U-5 - except in Synthesis Example 1, ?64 (0 〇18 mol) lactic acid, 8.00 g (0.054 mol) 2 , 2-bis(hydroxyindenyl)butyric acid (1) MBA) and 15.38 g (0-096 mol) of glycerol monomethacrylate were changed to i 9 g (〇^ 莫) malic acid, 8.4 g (〇.〇6 mol) 2,2·bis(hydroxymethyl)propionic acid (DMPA), 12.7 g (0. 8 mol) glycerol monodecyl acrylate, 10-6 g (0.01 mol) polypropylene glycol 1 〇 2 g (〇〇7 mol ) hexamethylene diol, changing 73 g of cyclohexanone to 6 〇 g, 30.03 g (0.12 mol) of 4,4, diphenylmethane diisocyanate (MDI) and 4.80 g (0.03 mol) I,4-phenylene diisocyanate (pDI) was changed to 48.1 g (0-19 mol) of 4,4'-diphenylmethane diisocyanate (MDI) and 8.1 g (0.05 mol) of hexamethylene diisocyanate ( Other than HMDI), a polyurethane resin U-5 solution (solid content: 45 mass%) represented by the following formula was synthesized in the same manner as in Synthesis Example 1. The solid content of the obtained polyamino phthalate resin U-5 solution was 48 mg KOH/g. The weight average molecular weight (polystyrene standard) measured by gel permeation chromatography (Gpc) was 11, 〇 Hey. &lt;Polyurethane resin U-5&gt; However, in the above formula, a5, b5, c5, d5, e5, f5 and h5 represent a composition ratio (% by mass). (Synthesis Example 6) - Synthesis of polyamino phthalate resin U-6 _ 48 - 201209066 In addition to Synthesis Example 1, 1.62 g (0-018 mol) of lactic acid, 8.〇〇g (〇.〇54) Molar) 2,2_bis(transmethyl)butyric acid (dmba) and 15.38 g (0.096 mol) glycerol monomethacrylate were changed to 29 g (〇〇2 mol) citric acid, 9.4 g (〇 〇7 mol) 2,2·bis(hydroxyindenyl)propionic acid (DMPA) and 28.9 g (0.18 mol) of glycerol monodecyl acrylate, 73 g of cyclohexanone was changed to 63 g, 30.03 g ( 0.12 mol) 4,4,-diphenylmethane diisocyanate (MDI) and 4.80 g (0.03 mol}1,4-phenylene diisocyanate (pDI) were changed to 37.7 g (0.15 mol) 4,4 A polyamino group represented by the following formula was synthesized in the same manner as in Synthesis Example 1, except that diphenylmethane diisocyanate (MDI) and dimercaptohexamethylene diisocyanate (TMHDI) 2i_ig (01 mmol) were used. Formic acid from the resin U-6 solution (solid content: 45% by mass). The solid content of the obtained polyamino phthalic acid vinegar resin U-6 solution was 63 mgKOH/g' as measured by gel permeation chromatography (Gpc). Weight average molecular weight (polystyrene standard) 16, 〇〇〇 &lt;. Yue poly amino ester resin U-6 &gt;

However, in the above formula, a6, b0, d0, and h0 represent the composition ratio (% by mass). (Synthesis Example 7) &lt;Synthesis of Polyurethane Resin U-7-Synthesis of Carboxylic Acid Compound (A) - 49-201209066 3-neck round bottom flask equipped with a condenser and a 1 L of a mixer 73.8 g (0.55 mol) of 2,2-bis(methylidene)propionic acid (Dmpa), and 99_ lg (0.5 mol) of hydrogenated trimellitic acid (manufactured by Mitsubishi Gas Chemical Co., Ltd.) was added to 400 mL. Tetrahydrofuran (THF) 'at 6 〇. (: stirring for 8 hours. After completion of the reaction, the reaction solution was added dropwise to 2 L of hexane to precipitate crystals. After standing for 1 ,, the solid was collected by filtration, and vacuum-dried to obtain a carboxylic acid compound (A) represented by the following formula: 158.6 g. &lt;Carboxylic acid compound (A)&gt;

T COOH ^ΛγΟν^Ι^ΟΗ • Synthesis of polyamino phthalate resin υ-7 _ In addition to Synthesis Example 1, 1.62 g (〇.〇i8 mol) lactic acid, 8.00 g (0.054 mol) 2 , 2-bis(transmethoxy)-butyric acid (DMBA) and 15.38 g (0.096 mol) of glycerol monomethacrylate were changed to 94 g (〇〇i Mo) retarding compound (A), 4.9 lg ( 〇.〇3莫耳) 2,2-bis(p-carbyl)butyric acid (DMBA), 17.43g (0.u molar) glycerol monomethyl acrylate vinegar with 10.99g (0.0 3 mole) Hexamethylene glycol, changing 73 g of cyclohexanone to 61 g, 3 0.0 3 g (0.12 簟:§:, &lt;,, μ, ear) 4,4-dicarbyl methane diisocyanate (MDI) 4.80g (〇.〇3莫耳,]/甘兴斗) 1,4-extension base diisocyanate (pdi) was changed to 53.27g (0.21 mol) 4,4 and 3.98g (0.02 mol) hexa and synthesis In the same manner as in Example 1, an ester resin U-7 solution (solid content of diphenylnonane diisocyanate (MDI) methyl diisocyanate (HMDI) was synthesized, and 45 mass% of polyamine decanoic acid represented by the following formula was synthesized). -50- 201209066 The solid content of the obtained polyamino phthalate resin u_7 solution is 66 mgKOH/g', and the weight average molecular weight (polystyrene standard) measured by gel permeation chromatography (Gpc) is 12. Hey. &lt;Polyuryl phthalate resin u-7&gt;

HOOC

COOH d, f, and k represent the composition ratio (Synthesis Example 8) - Synthesis of polyamino phthalate resin υ-χ - except in Synthesis Example 1, '1.62 g (0.018 mol) lactic acid, 8.00 g ( 0.054 mol) 2,2-bis(fluorenyl)butyric acid (DMBA) and 15.38 g (0-096 mol) glycerol monomethacrylate were changed to 16.7 g (0.12 mol) 2,2-dual Propionate (DMpA) with 26.8 g (0.17 mol) of glycerol monodecyl acrylate, 73 g of cyclohexanone was changed to 67 g, 30.03 g (0.12 mol) of 4,4'-diphenyl Methane diisocyanate (MDI) with 4.80 g (0.03 mol) 丨, 4 phenyl diisocyanate (pDI"^39.3 g (0.16 mol) 4,4'-diphenylnonane diisocyanate (MDI) The polyamino phthalate resin UX solution (solid content: 45 mass%) represented by the following formula was synthesized in the same manner as in Synthesis Example 1, except that 17.6 g (0.10 mol) of hexakirylidene diisocyanate (HMDI). The solid content of the polyacrylic acid S resin υ·χ solution has an acid value of 72 mg KOH/g, and the weight average molecular weight (polystyrene standard) measured by gel permeation chromatography (Gpc) is 8,500. -51 - 201209 066

Hr Ί r

H

Ja10

, j0一^0—L 〇il0 O^OH c10 ,. In the above formula, 'alO, blO, clO, and dlO are the composition ratios (% by mass). (Synthesis Example 9) - Synthesis of polyamino phthalate resin U - Y - In addition to Synthesis Example 1, '1.62 g (0.018 mol) of lactic acid, 8-〇〇g (0.054 mol) 2,2- Bis(hydroxyindenyl)butyric acid (DMBA) and 15.38 g (0.096 mol) of glycerol monodecyl acrylate were changed to 16_2 g (〇.〇9 mol) polytetramethylene glycol and 523 g (〇〇9 mol) 22 Bis(hydroxyindenyl)propionic acid (DMPA), 73 g of cyclohexanone was changed to 65 g, 30_03 g (0-1 mol) of 4,4'-diphenyldecane diisocyanate (MDI) and 4_80 g (0. 3 mol), 4_phenylene diisocyanate (pDI) was changed to 33_2 g (0.14 mol) of 4,4'-diphenyldecane diisocyanate (Mdi) except that the synthesis was carried out in the same manner as in Synthesis Example 1. Polyurethane carboxylic acid resin UY solution (solid content: 45 mass%) represented by the following formula. The solid content of the obtained polyamino phthalate resin υγ solution was 75 mgKOH/g', and the weight average molecular weight (polystyrene standard) measured by gel permeation chromatography (GpC) was 8,2 Å. <Polyamine phthalate resin υ-γ> 1 Η Η

-52-201209066 However, in the above formula, a1, bl1, and cl1 represent a composition ratio (% by mass). (Synthesis Example 10) - Synthesis of polyamino phthalate resin UZ - except in Synthesis Example 1, '1.62 g (0.01 8 mol) lactic acid, 8.00 g (0.054 mol) 2,2-dual ( Butyl acid (DMBA) and 15.38 g (0.096 mol) of glycerol monomethyl acrylate were changed to 0.89 g (0.007 mol) malic acid, 8.05 g (0.06 mol) 2,2- Bis(methylidene)propionic acid (DMPA), 33.51g (0.033 mol) polypropylene glycol (PPG1000) and hexamethylene diol 7, 〇8g (〇.〇61 mol), 73g of cyclohexane The ketone was changed to i〇3g, and 30.03g (0.12 mole) of 4,4,-diphenyldecane diisocyanate (MDI) and 4.80g (0.03 mole) of ι,4-phenylene diisocyanate (?1) 1) Changed to 20.85 g (0.083 mol) of 4,4,-diphenyldecane diisocyanate (MDI) and 14.02 g (0.083 mol) of hexamethylene diisocyanate (HMDI), and Synthesis Example 1 In the same manner, a polyamine-based 曰k S 曰 resin U-Z solution represented by the following formula (solid content: 45 mass%) was synthesized. The solid content of the polyurethane-based resin u_z solution was 40 mgKOH/g', and the weight average molecular weight (polystyrene standard) measured by gel permeation chromatography (Gpc) was 18, 〇〇〇. <polyamine phthalate resin U-Z&gt; b7 [〇如罐 η

However, in the above formula, a7, b7, c7, e7, f7 and h7 represent the composition ratio (% by mass). -53-201209066 (Synthesis Example 11) - Synthesis of polyester resin El - In a reactor, 6.9 parts by mass of p-nonanoic acid diammonium dicarboxylate and 226 parts by mass of diammonium adipate were mixed in a reactor. Dinonyl dicarboxylate, 417 parts by mass of 2,2-didecyl heptane parts by weight of butanediol, 769 parts by mass of ethylene glycol, Irganox 1 330 as a chemical agent (Ciba Japan shares limited parts of tetrabutyl phthalate) After stirring for 2 hours at 260 ° C, and then heating at 260 ° C for 1 hour to carry out the ester exchange, the reactor is slowly depressurized and simultaneously heated, and the temperature is 30 ° C, 0.5 to 2 torr for the initial polycondensation reaction. After the polymerization reaction was carried out for 4 hours in the state of 0.5 to 2 torr, the pressure was returned to atmospheric pressure for 30 minutes, and the polyester was taken out as pelletized fat E-1. The obtained dilution was dissolved in propylene glycol monodecyl ether acetate. A solid content concentration of 60% by mass was obtained to obtain a solution. The obtained polyester resin E-1 had a gel permeation chromatography average molecular weight (polystyrene standard) of 34,000. (Example 1) - Production of photosensitive film - Coating sensitization on the thickness of 16 μm η as a support body (made by Toray Co., Ltd., 16 FB50) The composition solution 1 was dried to a photosensitive layer having a thickness of 30 μm. A polypropylene film (Prince Special Paper Co., Ltd. Ε-200) was laminated on the photosensitive layer to obtain a photosensitive film. Methyl ester, 524-ester ester, 553 mass i alkanediol, 324 2 parts by mass of anti-oxidation company), 0.9 temperature rise from room temperature to hydrazine reaction. Then, 245 I was made in minutes, and dry nitrogen was introduced at 245 ° C to obtain a weight measured by the polyester tree polyester resin E-1 丨 polyester resin E-1 method.

The ethylene glycol diester film is formed on a support having the following composition to form a composition having a thickness of 20 μm, ALPHAN-54-201209066 - photosensitive composition solution 1 - • Polyamine phthalate resin U-1 solution of Synthesis Example 1. (solid content: 45 mass%) · · ·37.2 parts by mass • Polymerizable compound (A-DPH, manufactured by Shin-Nakamura Chemical Co., Ltd.) · · · 1.1 1.1 parts by mass • Thermal crosslinking agent (Epotohto YDF-170, Dongdu Chemical Co., Ltd., bisphenol F-type epoxy resin) · · · 2.0 parts by mass • Photopolymerization initiator represented by the following structural formula C-1...1.0 parts by mass

C-1 • Diethyl 9-oxosulfuron··· 0.7 parts by mass • Pigment dispersion (hereinafter referred to as “G-1”)··································· 30% by mass of mercaptoethyl ketone solution (manufactured by Industrial Co., Ltd.)··· 1. 1 3 parts by mass • mercapto ethyl ketone (solvent) · · · 1 2.0 parts by mass, the aforementioned pigment dispersion (G -1) 30 parts by mass of premixed vermiculite (manufactured by Admatech Co., Ltd., SO-C2), 8.2 parts by mass of the polyurethane resin U-1 solution of Synthesis Example 1, and 0.51 parts by mass of indigo blue 0.14 parts by mass of lanthanide yellow pigment (CIPY24) and 59.0 parts by mass with cyclohexanone, 'Motor Mill M-250 (manufactured by EIGER), yttrium oxide beads with a diameter of 〇mm, at a peripheral speed of 9 m /s was dispersed for 3 hours for modulation. -55-201209066 - Lamination of the base body - The surface of the copper clad laminate (no through hole, copper thickness 12 μηι) was subjected to chemical polishing treatment as the above-mentioned substrate. In the copper-clad laminate, the photosensitive layer of the photosensitive film is brought into contact with the copper-clad laminate, and a vacuum laminator (manufactured by Nichigo-Mcmon Co., Ltd.) is used while peeling off the protective film of the photosensitive film. And νρΐ3〇), which is laminated to form a laminate of the copper-clad laminate, the photosensitive layer, and the polyethylene terephthalate film (support). The pressing condition is a vacuum suction time of 4 〇 seconds, and a pressure temperature of 7 〇. 〇, press pressure 0_2MPa, pressurization time 1 〇 second. The obtained laminate was evaluated for surface hardness, fine pattern formability, resolution, insulation, development residue removal property, heat resistance, and toughness as follows. The results are shown in Table 1. &lt;Measurement of Surface Hardness&gt; A solder resist layer containing each photosensitive composition was formed on a substrate. When the load was applied at a load of 1 kg in accordance with the test method of JIS K-5400 and a pencil hardness tester, the highest hardness which does not cause scratches on the film was evaluated in accordance with the following criteria. [Evaluation Criteria] 〇: When the surface hardness exceeds 4H, the surface hardness is excellent Δ : 3H to 4H 'The surface hardness is slightly inferior x: 2H or less, the surface hardness is poor. <Evaluation of fine pattern formation property> In order to evaluate the permanent pattern produced The fine pattern formation in the shape, and the photosensitive layered body after the formation of the permanent pattern is cut off, and the scanning type: 56-201209066 $ submicroscope (S-4100, manufactured by Hitachi, Ltd.), from the first! The cross-section of the pattern 1 is shown in the figure, and the angle Θ between the face 2 on the side of the support and the side 3 of the permanent pattern is observed in cross section. [Evaluation Criteria] ◎: The angle Θ is 80. Small 〇: The angle Θ is 80. Above is less than 90. 〇△: The angle Θ is 90. The above is less than ι00 〇 △: the angle Θ is 1〇〇. The above is less than 11 inches. x: The angle Θ is 11〇. The above-mentioned 'analytical evaluation> The above-mentioned photosensitive laminate was allowed to stand at room temperature (23 ° C) and 55% RH for 1 Torr to obtain a polyethylene terephthalate film from the obtained photosensitive laminate ( On the support, use a circular hole pattern, using a pattern forming device, and exposing at the optimum light energy, so that a circular hole having a diameter of 5 〇μπι 2 2 〇〇μϊη can be formed. t After standing at room temperature for 1 〇 minutes Stripping the polyethylene terephthalate film (support) from the photosensitive laminate. The total thickness of the photosensitive layer on the copper-clad laminate is 0.1 μm, the shortest development time #2 times the time Developing solution 3 (rc 1 mass% aqueous sodium carbonate solution, dissolving and removing the unhardened region. Observing the surface of the steel clad laminate with the hardened resin pattern thus obtained by an optical microscope;; there is no curl or peeling of the pattern portion, etc. In addition, the minimum circular hole pattern width of the gap can be regarded as the untwisting, and the evaluation is performed based on the following criteria. Bamboo [Evaluation Criteria] ◎: A circular hole having a diameter of 80 μm or less can be analyzed, and the analytical property is excellent -57-201209066 〇: Resolvable diameter 1〇〇μπι The following Δ: the resolution of the circle having a diameter of 200 μm or less is good. χ : The hole is not analyzed, and the analytical poor hole is slightly poorly analyzed. <Evaluation of insulation> The copper foil having a thickness of 12 μm is laminated on the substrate. The copper box is etched, and the substrate is printed as 5 〇/50 陶, the wires are not in contact with each other, and a comb-shaped electrode having a mutual edge/gap width is obtained. The common method is in the base 2: the same-planar agent The layer was exposed to the optimum exposure amount (3. 芏 y* a, w J/cm). After the person was allowed to stand for 1 hour under the dish, it was sprayed and developed with an aqueous solution of 3 〇〇c. Second, sodium sate, 1 λ 八 a also v in 80 C plus (teaching • Μ J / cm of energy on the photosensitive layer UV irradiation. $ _ light layer in l5 〇 t heat treatment 6G minutes, borrow This was used to prepare a substrate for evaluation of a solder resist. ^Using Sn/pb solder to connect a shielded wire made of polytetrafluoroethylene to a comb-shaped electrode so that a voltage can be applied to the heated laminated layer. Between the comb-shaped electrodes of the body, the evaluation was carried out in a state where a voltage of 5 V was applied to the laminated body for evaluation. The layer body was allowed to stand in the ultra-accelerated high-temperature and high-humidity test (HAST) tank of 13 〇, 8 5% RH for 2 。 hours. The solder resist of the laminate for evaluation was observed by a 100-fold metal microscope. [Improvement of the migration] [Evaluation criteria] ◎: The occurrence of the offset was not confirmed, and the insulation was excellent. 〇: Although the offset was slightly observed on the copper, the insulation was good. -58-201209066 Poor insulation. Insulation resistance Δ: The occurrence of the offset was confirmed, and x: a short circuit occurred between the electrodes. &lt; Evaluation of the development residue removal property The bottom residue of the round holes of 80 μm and 120 μm in the analytical evaluation sheet was observed by SEM. The obtained surface of the hardened resin pattern has no residue or residue at the bottom of the round hole of the measurement pattern; an abnormality such as peeling, and a fear of opening the gap, and a circular hole pattern formed by evaluation of the circle and the circle is observed by an optical microscope. The table of the multi-layer steel laminate has the curl of the file section and the width of the circle pattern, and

[Evaluation Criteria] ◎: There is no development residue on the substrate having a circular hole diameter of 8 〇μΐη, and the development residue is excellent in removability. 〇: There is no _ shadow residue on the substrate having a circular hole diameter of 120 μm, and the development residue has good removal property Δ: There is a slight development residue on the substrate which is directly passed through a circular hole of 120 μΐη, and the development residue is slightly deteriorated. X: Development residue is present on the substrate having a circular hole diameter of 120 μm, and the development residue is poorly removed. &lt;For thermal properties&gt; The solder resist layer formed of each photosensitive composition was coated with a rosin-based flux to form an evaluation substrate, which was immersed in a solder bath set at 260 ° C for 30 seconds to modify the alcohol to clean the flux. Thereafter, the expansion, peeling, and discoloration of the visible photoresist layer were evaluated in accordance with the following criteria. [Evaluation Criteria] -59- 201209066 ◎: It is confirmed that there is no change at all, and the heat resistance is excellent. Although the expansion, peeling, and discoloration are slightly found, the heat resistance is excellent. △: Although it is found that expansion and peeling are found, it is heat resistant. Good △: Partial expansion and peeling are observed, and heat resistance is poor X: Expansion and peeling of the coating film &lt;Strength and toughness&gt; On a printed circuit board formed by breaking a glass epoxy substrate with a thickness of 12 μ? In the conventional method, the photosensitive layered body having the solder resist layer is formed, and a 2 mm square mask is used to make the hmw-201 GX type exposure machine manufactured by the 〇 rc rc, so as to form an optimum exposure amount of the 2 _ square pattern (3 〇 〇m Wm W) Exposure. Then, after standing at room temperature for 1 hour, 'α 30K1% by mass aqueous sodium carbonate solution was spray-developed for 60 seconds, and further heated at 8 (rc) for 1 minute. After the absence, =RC produced the ultraviolet irradiation device, The energy of the iw is irradiated with ultraviolet rays. The substrate for evaluation is formed by further adding the photosensitive layer in the 15th generation for 60 minutes to form a substrate having a rectangular open solder resist of 2 Å square. After 15 minutes of exposure, then, after a large exposure of ^0C for 15 minutes, it was again thermally cycled in the atmosphere of (10). The degree of pass was observed by an optical microscope, and the following "pre-existing soil:: cracks on the flux (cracked) and Peeling process [Evaluation criteria] ◎•Resistance flux without cracks (cracked), peeling, strong thief-excellent -60- 201209066 Although the solder resist has some cracks (cracked) or good system peeling, the toughness is slightly poor Peeling, poor toughness △: some cracks in the solder resist (cracking X: obvious cracks in the solder resist (cracking), (Example 2) bottle of Hanshui and pattern manufacturing photosensitive film, laminated ~ double transport, Hanping price · r ^Example In addition, except the polyaminocarbamic acid cool tree of the synthesis example 1 and the gluten solution (solid content: 45 mass%) were replaced by the polyamine|formic acid of the synthetic resin U-2 solution (solid content: 45 mass%). In the same manner as in Example 1, the photosensitive material was supplied to the dTtr, the laminate, and the permanent film. The obtained laminate was subjected to surface hardness and micro-name field in the same manner as in Example 1. Evaluation of properties, characterization, insulation, development residue removal, resistance to 'I*, ^, and toughness. The results are shown in Table 1. (Example 3) 4 Manufacture of film, laminate, and permanent pattern And evaluation - In the first embodiment, 'the polyamine of Synthetic Example 3 was replaced with the polyamine of Synthetic Example 3 except that the polyurethane of Synthetic Example 1 was used for Ij, 1 'yield> (solid content: 45 mass%) In the same manner as in Example 1, except that the film was formed in the same manner as in Example 1, the photosensitive film, the laminate, and the layered product were obtained in the same manner as in Example 1. Surface hardness, fine pattern, difficulty forming, resolution, insulation, development residue, heat resistance, Evaluation of the toughness. The results are shown in Table 1. (Example 4) -61 - 201209066 - Production and evaluation of photosensitive film, laminate, and permanent pattern - In Example 1, except for Synthesis Example 1, The polyamino phthalate resin U-1 solution (solid content: 45 mass%) was replaced with the polyamino phthalate resin U-4 solution of Synthesis Example 4 (solid content: 45 mass%), and the same procedure as in Example 1 was carried out. The photosensitive film, the laminate, and the permanent pattern were obtained, and the obtained laminate was subjected to surface hardness, fine pattern formation property, resolution, insulation, development residue removal property, heat resistance, and strength in the same manner as in Example 1. Evaluation of resilience. The results are shown in Table 1. (Example 5) - Production and evaluation of photosensitive film, laminate, and permanent pattern - In Example 1, except that the polyurethane resin U-1 solution of Synthesis Example 1 was used (solid content: 45 mass) In the same manner as in Example 1, except that the polyurethane resin U-5 solution of Synthesis Example 5 (solid content: 45 mass%) was used, a photosensitive film, a laminate, and a permanent pattern were obtained. The obtained laminate was evaluated for surface hardness, fine pattern formation property, analytical property, insulating property, development residue removal property, heat resistance, and toughness in the same manner as in Example 1. The results are shown in Table 1. (Example 6) - Production and evaluation of photosensitive film, laminate, and permanent pattern - In Example 1, except that the polyurethane resin U-1 solution of Synthesis Example 1 was used (solid content: 45 mass) In the same manner as in Example 1, except that the polyurethane resin U-6 solution (solid content: 45 mass%) of Synthesis Example 6 was used, a photosensitive film, a laminate, and a permanent pattern were obtained. -62- 201209066 The resulting laminate was subjected to lamp surface hardness, micro', pattern formation, analyticity, insulation, lithography, removal of the residue, and resistance to the residue. Evaluation of sexuality, strength and toughness. The results are shown in Table i. (Example 7) The production and evaluation of the photosensitive film, the laminate, and the permanent pattern were carried out in the same manner as in Example 1 except that the photosensitive composition solution 丨 was replaced with the photosensitive composition solution 2, and Examples The same process is carried out to obtain a photosensitive film, a laminate, and a permanent pattern. In the same manner as in Example 1, the obtained laminate was evaluated in terms of surface hardness, fine darkness, V formation property, resolution, insulation property, development residue removal property, and profitability. The results are shown in Table 1. The composition of the light-sensitive composition solution 2 - The photosensitive composition solution 2 was prepared by considering the following components. - Polyamine phthalate resin U-4 solution of Synthesis Example 4 (solid content: 4 S mass%) · · · 20.3 parts by mass • Polymerizable compound: DCP-A (manufactured by Kyoei Chemical Co., Ltd.) · · S·3 parts by mass 2.9 • Thermal cross-linking agent: Epotohto parts by mass YDF-170 (manufactured by Tosho Kasei Co., Ltd.) · · · Starting agent: Irgacure 907 (manufactured by BASF) ···〇.6 parts by mass Agent: DETX-S (manufactured by Sakamoto Chemical Co., Ltd.) · · · 〇·〇〇 5 parts by mass • Reagent: EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) ························· "G-2") · · · 30·1 parts by mass of coating aid: Megafac F-780F...0.2 parts by mass -63- 201209066 (made by Otsuka Ink Chemical Industry Co., Ltd.: 30% by mass of mercaptoethyl Ketone solution) • Elastomer: Polyester resin Ε-1 of Synthetic Example 11 (solid content: 60% by mass) · · ·2.7 parts by mass Further, the above pigment dispersion (G-2) is made by Shimaishi (Admatech Co., Ltd.) , SO-C2) 32.0 parts by mass, Soluspass 24000GR (manufactured by Lubrizol Co., Ltd.) 0.44 parts by mass, and the polyurethane urethane resin U-4 solution of Synthesis Example 4 (solid content: 45 mass%) 12.0 Mass parts, 0,21 parts by mass of ochre blue, 0.06 parts by mass of lanthanide yellow pigment (CIPY24), 1.65 parts by mass of IXE-6107 (manufactured by Toagosei Co., Ltd.), 0.35 mass of melamine (manufactured by Wako Pure Chemical Industries, Ltd.) The mixture was preliminarily mixed with 77.4 parts by mass of cyclohexanone, and then prepared by using a Mill Mill M-250 (manufactured by EIGER Co., Ltd.) and dispersing the beads at a peripheral speed of 9 m/s for 3 hours at a peripheral speed of 9 m/s. (Example 8) - Production and evaluation of photosensitive film, laminate, and permanent pattern - In addition to Example 7, the polyaminocarbamate resin U-4 solution of Synthesis Example 4 (solid content: 45 mass%) In the same manner as in Example 7, except that the polyamino phthalate resin U-5 solution (solid content: 45 mass%) of the synthesis example 5 was changed, a photosensitive film, a laminate, and a permanent pattern were obtained. The obtained laminate was evaluated for surface hardness, fine pattern formability, resolution, insulation, development residue removal, heat resistance, and strongness in the same manner as in Example 1. The results are shown in Table 1. (Example 9) - Production and evaluation of photosensitive film, laminate, and permanent pattern - 64 - 201209066 In addition to Example 7 t, the polyamino phthalate resin ϋ-4 solution of Synthesis Example 4 was used ( A photosensitive film, a laminate, and a film were prepared in the same manner as in Example 7 except that the polyamine phthalate resin U-7 solution (solid content: 45 mass%) of the synthesis example 7 was used. Permanent pattern. The obtained laminate was evaluated for surface hardness, fine pattern formation property, analytical property, insulating property, development residue removal property, heat resistance, and toughness in the same manner as in Example 1. The results are shown in Table 1. (Example 1 〇) - Production and evaluation of photosensitive film, laminate, and permanent pattern - In addition to Example 7, a thermal crosslinking agent (Ε ρ 〇t 〇ht 〇 YDF-1 70, Dongdu was formed In the same manner as in Example 7, except that a thermal crosslinking agent (TECHMORE VG-3 101, manufactured by Printec Co., Ltd., bisphenol condensation type epoxy resin) was used instead of the company's bisphenol F-type epoxy resin. A photosensitive film, a laminate, and a permanent pattern were obtained. The obtained laminate was evaluated for surface hardness, fine pattern formation property, analytical property, insulating property, development residue removal property, heat resistance, and toughness in the same manner as in Example 1. The results are shown in Table 1. (Comparative Example 1) - Production and evaluation of photosensitive film, laminate, and permanent pattern - In Example 1, except that no thermal crosslinking agent was added (Epotohto YDF-1 70, manufactured by Tohto Kasei Co., Ltd., double A photosensitive film, a laminate, and a permanent pattern were produced in the same manner as in Example 1 except for the phenol f-type epoxy resin. -65-201209066 The obtained laminate was evaluated for surface hardness, fine pattern formability, resolution, insulation, development residue removal property, heat resistance, and toughness in the same manner as in Example 1. The results are shown in Table 1. (Comparative Example 2) - Production and evaluation of photosensitive film, laminate, and permanent pattern · In Example 1, except that the polyamino phthalate resin U-1 solution of Synthesis Example 1 was used (solid content 45) A photosensitive film, a laminate, and a permanent pattern were produced in the same manner as in Example 1 except that the polyurethane resin UZ solution (solid content: 45 mass%) of the synthesis example 10 was used. The obtained laminate was evaluated for surface hardness, fine pattern formation property, analytical property, insulating property, development residue removal property, heat resistance, and toughness in the same manner as in Example 1. The results are shown in Table 1. (Comparative Example 3) - Production and evaluation of photosensitive film, laminate, and permanent pattern - In Example 1, except that the polyamino phthalate resin U-1 solution of Synthesis Example 1 was used (solid content: 45 mass) In the same manner as in Example 1, except that the polyamine phthalate resin UX solution (solid content: 45 mass%) of Synthesis Example 8 was used, a photosensitive film, a laminate, and a permanent pattern were obtained. The obtained laminate was evaluated for surface hardness, fine pattern formation property, analytical property, insulating property, development residue removal property, heat resistance, and toughness in the same manner as in Example 1. The results are shown in Table 1. (Comparative Example 4) - Production and Evaluation of Photosensitive Film, Laminate, and Permanent Pattern - 66-201209066 In Example 1, except for the polyamine lipid U-1 solution of Synthesis Example 1 (solid content 45) The mass %) was replaced by the synthesis example phthalate resin UY solution (solid content: 45 mass%) in the same manner as in Example 1, to obtain a photosensitive film or a laminate pattern. The obtained laminate was evaluated for surface fine pattern formability, resolution, insulation, development residue heat removal property, and toughness in the same manner as in Example 1. The results are shown in Table 1.聚 ® 旨 旨 的 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 1 U-2 U-3 U-4 The presence or absence of a carboxyl group at the end of the main chain (number) Yes (1) Yes (2) Yes (2) Yes (1) The presence or absence of a side chain ethylenically unsaturated group There are thermal cross-linking agents YDF-170 YDF-170 YDF-170 YDF-170 Evaluation results Surface hardness 〇〇〇〇 Fine pattern formation 〇 ◎ ◎ ◎ Analytical ◎ ◎ ◎ ◎ Insulation 〇 ◎ 〇〇 Development residue Removability ◎ ◎ ◎ ◎ Heat resistance and toughness 〇〇〇〇 [Table 1-2] Example 5 Example 6 Example 7 Example 8 Testability Resin type U-5 U-6 U-4 U-5 The presence or absence of a carboxyl group at the end of the main chain (number) There are (2) Yes (3) Yes (1) Yes (2) In the side chain, the ethylenically unsaturated group has or is thermally crosslinked. YDF-170 YDF-170 YDF-170 YDF-170 Evaluation results Surface hardness 〇〇〇〇 Fine pattern formation Square ◎ ◎ ◎ ◎ ◎ ◎ Analyticity insulating ◎ square development residue removability ◎ ◎ ◎ ◎ ◎ ◎ heat resistance square square square square square square toughness ◎ ◎ -68- 201209066 [Table 1-3]

Example 9 Example 10 Examination of the type U-7 U-4 The presence or absence of a carboxyl group at the end of the main chain (number) Yes (3) Yes (1) The presence or absence of a resin in the side chain ethylenically unsaturated group Thermal cross-linking agent YDF-170 VG-3101 Surface hardness 〇〇 Evaluation result Fine pattern formation 〇〇 Analytical ◎ 〇 Insulation 〇〇 Development residue removal ◎ ◎ Heat resistance 〇 ◎ Strong ◎ 〇 [Table 1 4] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Alkali display. Type U-1 UZ UX UY The presence or absence of a carboxyl group at the end of the main chain (number) Yes (1) Yes (2) No resin-free *&quot;'----- The presence or absence of a side chain ethylenically unsaturated group with or without a thermal crosslinking agent No YDF-170 YDF-170 YDF-170 Surface hardness 1 XX 〇〇 Evaluation result Fine pattern formation 〇 △ 〇 Δ Δ Δ analytical 〇〇〇〇 insulation X Δ Δ Δ development residue removal 〇〇 Δ Δ heat X Δ 〇 Δ strong toughness X 〇〇 X From the results of Table 1, it is known that compared with Comparative Examples 1 to 4 ratio Example 1 removed high system development residue, a fine pattern can be formed, and analytical properties, heat resistance, strength and toughness and excellent in the insulating property thereof. -69-201209066 [Industrial Applicability] The photosensitive composition of the present invention is particularly suitable for use because it has a high development residue residue and can form a fine pattern and is excellent in heat resistance, toughness, resolution, and insulation. Solder resist. Since the photosensitive film of the present invention can form a high-definition permanent pattern efficiently, it can be suitably used for various pattern formations such as a permanent pattern of a protective film, an interlayer insulating film, a solder resist pattern, etc., BGA (Ball Grid Array), Manufacturing of a liquid crystal structural member such as a semiconductor package for forming a CSP (wafer size package) or a TCP (tape package), a color filter, a pillar, a rib, a spacer, a partition, or the like, a full picture, and a micro The manufacture of a machine, a proof, etc. is particularly suitable for the formation of a permanent pattern for a printed circuit board, a BGA (Ball Grid Array), a CSP (wafer size slash, a Tcp (a tape-type package, etc.). The water of the present invention. The long pattern forming method is suitable for use in semiconductor package formation, protective film, interlayer insulation, such as BGA (Ball Grid Array), csp (Wafer Size Package), TCP (Tape Tape Package), etc., because the photosensitive composition is used. Liquid crystal structures such as various patterns for forming a permanent pattern such as a film and a solder resist pattern, a coloring house, a smear, a pillar, a rib, a spacer, a partition wall, and the like Manufacturing of components ~41 dry springs, kings, micro-machines, proofs 1 &amp; 4 'especially suitable for 7 , σ for brushed substrate permanent pattern BGA (ball grid array), c crystal and other semiconductor seals The formation of the attack. Magic TCP (tape-wrapped package) [Simple description of the drawing] Figure 1 is a diagram of the shape of the pattern that does not seek for a long time. -70- 201209066 [Description of the main components] 1 Support body 2 The surface of the support side 3 permanent pattern side 10 permanent pattern 爽 refreshing angle-71-

Claims (1)

201209066 VII. Patent application scope: 1. A photosensitive composition comprising a developing composition, a polymerizable compound, a photopolymerization initiator and a thermal crosslinking agent, characterized in that: Resin selected _ 士士&amp;# w波饰精聚基基酯酯基的聚基酸酸树脂树脂, and at least the main chain end of the 平 * ♦ and ♦ amino-based f-ester resin has at least One was recorded, &amp; + residue and had an ethylenic group in the side chain. 2. The photosensitive composition according to claim 1, wherein the polymer chain has two or more and five or less groups at the terminal end of the main chain. 3. The photosensitive composition of claim 1, wherein the terminal of the main chain of the urethane resin has a structure represented by the following general formula (1), -L1 - (COOH)n · · · general formula (I In the general formula (I), 'L1' indicates that the (n+1)-valent organic linkage η represents an integer of 1 or more. 4. The photosensitive composition of claim 1, wherein the dominant tree has a slow-developing developable unit in a side chain of the polyamino phthalic acid-based resin. The photosensitive composition of the four items is represented by the formula (II), and the general formula (H) COOH amine amine and amine carboxylamine 5. The patented range unit is the following R1 r^c ^r3 影影-72-201209066 3 Only in the general formula (11), R1 represents a hydrogen atom or a stimuli group, and R2 and R each independently represent a single bond, and may have an ether group, an ester group, or a guanamine group. Any of the alkyl sulfonate alkyl groups and the extended aryl groups which may have a carbonate group. The thief: only the photosensitive composition of the first paragraph of the patent scope of the patent, the neutral resin system, * has the structural unit represented by the following general formula (VI), General formula (VI) -C(CH3)2-, _S〇2_, _s_, _c〇 or _〇· ; γ represents _NH, -NHCO·, -NHCOO-, _C〇NH or 〇c〇NH; Rll, R12, R and R may be the same or different from each other, each representing a hydrogen atom, a monovalent organic group, a halogen atom, _〇ρ15 χτ, , , , L Λ , 〇,, 7 butyl, -N(R16) (R17 Or _SR18; R15 - Rl6, Rl7 and Rl8 represent a hydrogen atom or a valence organic group. 7. If you declare a patent reclamation! The photosensitive composition of the item, wherein the functional group having an ethylenically unsaturated group in the oxime is a (meth) propylene group. 8. The photosensitive composition according to the first aspect of the invention, wherein the alkali-developable resin is obtained by introducing a carboxylic acid compound having at least one carboxyl group at a terminal of a primary bond of a polyurethane resin. 9. The photosensitive composition of claim 1, wherein the alkali-developable resin is obtained by polymerizing a diisocyanate compound, a diol compound, and a carboxylic acid compound having at least one carboxyl group. -73- 201209066 10. The carboxylic acid compound of the patent application range is a dicarboxylic acid compound. The photosensitive composition, wherein the acidification is U. As claimed in the patent application, the acid ester composition is an aromatic photosensitive composition, wherein the diisocyanate is as described in the patent application. The photosensitive composition of the weight average molecular weight of the resin, wherein the alkali develops a photosensitive film, the amount is 5, _~6 〇, 〇〇〇. The photosensitive layer of the composition is obtained by having a photosensitive composition on the support. The photosensitive composition is a photosensitive resin, a human/V', a photopolymerization initiator, and a thermal crosslinking agent. , m曰 "synthesis of the testable resin thioglycolate resin, and ...: carboxylic acid hydroxy group and a polyamine group. Recorded, and has a photosensitive M.-type photosensitive laminate in the side chain, which is characterized by a photosensitive layer in the matrix composition, and a sensitizing substance containing the developing resin and the polymerizable compound. a polymerization initiator and a thermal crosslinking agent, wherein the alkali-developable resin is a polyamine-based resin which is linked by an amine group, and is in the main chain of the polyamine-based resin. The last U is a few bases and has an ethylenically unsaturated group in the side chain. 15. A permanent pattern forming method characterized by at least comprising: exposing a salt light layer formed of a photosensitive composition, the texture developing resin being a base phthalate resin, and at the end Has at least 1 thiol group. The permanent pattern of the next 201209066. The photosensitive composition contains an alkali-developing resin from the human body, and the condensing agent is used to start the 丨Τ» ～W and the thermal crosslinking agent, from the urethane group. And the polyurethane resin further has ethylene in the side chain. A printed substrate is characterized by, for example, forming a permanent pattern, the permanent pattern forming method comprising at least: a photosensitive layer formed by the inductive layer The photosensitive composition contains an alkali-developable resin, a polymer, a photopolymerization initiator, and a thermal crosslinking agent, and the test-developing resin is a urethane resin by an amino phthalic acid-based base. And having at least one buffer at the end of the polyphthalic acid ester resin and having an ethyl group in the side chain. Β-synthesis of polyamines, main chain end-unsaturation, formation method, photosynthetic composition, combined polyamine, main chain end-unsaturation, -75-