阅读说明：本技术 感光性树脂层叠体及其制造方法 (Photosensitive resin laminate and method for producing same ) 是由 加持义贵 于 2019-01-15 设计创作，主要内容包括：提供一种层叠体,其在基膜上具备感光性树脂组合物,所述感光性树脂组合物可以兼顾在显影液中的溶解性即显影性和对基板、特别是铜基板的密合性。一种感光性树脂层叠体,其特征在于,其具备支撑薄膜、和形成在支撑薄膜上的包含感光性树脂组合物的感光性树脂组合物层,感光性树脂组合物含有(A)碱溶性高分子；(B)具有烯属不饱和双键的化合物；(C)光聚合引发剂；及(D)铁原子,以感光性树脂组合物层为基准,感光性树脂组合物层中的铁原子的含量为0.01ppm以上且10ppm以下。(Provided is a laminate comprising a base film and a photosensitive resin composition provided thereon, wherein the photosensitive resin composition can satisfy both of developability, which is solubility in a developer, and adhesion to a substrate, particularly a copper substrate. A photosensitive resin laminate is characterized by comprising a support film and a photosensitive resin composition layer formed on the support film and containing a photosensitive resin composition, wherein the photosensitive resin composition contains (A) an alkali soluble polymer; (B) a compound having an ethylenically unsaturated double bond; (C) a photopolymerization initiator; and (D) iron atoms, the content of the iron atoms in the photosensitive resin composition layer is more than 0.01ppm and less than 10ppm based on the photosensitive resin composition layer.)

1. A photosensitive resin laminate comprising a support film and a photosensitive resin composition layer formed on the support film and containing a photosensitive resin composition,

the photosensitive resin composition contains:

(A) an alkali-soluble polymer;

(B) a compound having an ethylenically unsaturated double bond;

(C) a photopolymerization initiator; and

(D) an iron atom, a nitrogen atom, a fluorine atom,

the content of iron atoms in the photosensitive resin composition layer is 0.01ppm to 10ppm, based on the photosensitive resin composition layer.

2. The photosensitive resin laminate according to claim 1, wherein the content of iron atoms in the photosensitive resin composition layer is 0.1ppm or more based on the photosensitive resin composition layer.

3. The photosensitive resin laminate according to claim 1, wherein the content of iron atoms in the photosensitive resin composition layer is 0.2ppm or more based on the photosensitive resin composition layer.

4. The photosensitive resin laminate according to claim 1, wherein the content of iron atoms in the photosensitive resin composition layer is 0.3ppm or more based on the photosensitive resin composition layer.

5. The photosensitive resin laminate according to claim 1, wherein the content of iron atoms in the photosensitive resin composition layer is 0.4ppm or more based on the photosensitive resin composition layer.

6. The photosensitive resin laminate according to claim 1, wherein the content of iron atoms in the photosensitive resin composition layer is 0.5ppm or more based on the photosensitive resin composition layer.

7. The photosensitive resin laminate according to claim 1, wherein the content of iron atoms in the photosensitive resin composition layer is 0.6ppm or more based on the photosensitive resin composition layer.

8. The photosensitive resin laminate according to claim 1, wherein the content of iron atoms in the photosensitive resin composition layer is 0.7ppm or more based on the photosensitive resin composition layer.

9. The photosensitive resin laminate according to claim 1, wherein the content of iron atoms in the photosensitive resin composition layer is 0.8ppm or more based on the photosensitive resin composition layer.

10. The photosensitive resin laminate according to claim 1, wherein the content of iron atoms in the photosensitive resin composition layer is 0.9ppm or more based on the photosensitive resin composition layer.

11. The photosensitive resin laminate according to claim 1, wherein the content of iron atoms in the photosensitive resin composition layer is 1.0ppm or more based on the photosensitive resin composition layer.

12. The photosensitive resin laminate according to claim 1, wherein the content of iron atoms in the photosensitive resin composition layer is 2.0ppm or more based on the photosensitive resin composition layer.

13. The photosensitive resin laminate according to claim 1, wherein the content of iron atoms in the photosensitive resin composition layer is 3.0ppm or more based on the photosensitive resin composition layer.

14. The photosensitive resin laminate according to any one of claims 1 to 13, wherein the content of iron atoms in the photosensitive resin composition layer is 5.0ppm or less based on the photosensitive resin composition layer.

15. A photosensitive resin laminate according to any one of claims 1 to 11, wherein the content of iron atoms in the photosensitive resin composition layer is 2.0ppm or less based on the photosensitive resin composition layer.

16. The photosensitive resin laminate according to any one of claims 1 to 11, wherein the content of iron atoms in the photosensitive resin composition layer is 1.5ppm or less based on the photosensitive resin composition layer.

17. The photosensitive resin laminate according to any one of claims 1 to 10, wherein the content of iron atoms in the photosensitive resin composition layer is 1.0ppm or less based on the photosensitive resin composition layer.

18. The photosensitive resin laminate according to any one of claims 1 to 9, wherein the content of iron atoms in the photosensitive resin composition layer is 0.9ppm or less based on the photosensitive resin composition layer.

19. A photosensitive resin laminate according to any one of claims 1 to 8, wherein the content of iron atoms in the photosensitive resin composition layer is 0.8ppm or less based on the photosensitive resin composition layer.

20. A photosensitive resin laminate according to any one of claims 1 to 7, wherein the content of iron atoms in the photosensitive resin composition layer is 0.7ppm or less based on the photosensitive resin composition layer.

21. A photosensitive resin laminate according to any one of claims 1 to 6, wherein the content of iron atoms in the photosensitive resin composition layer is 0.6ppm or less based on the photosensitive resin composition layer.

22. A photosensitive resin laminate according to any one of claims 1 to 5, wherein the content of iron atoms in the photosensitive resin composition layer is 0.5ppm or less based on the photosensitive resin composition layer.

23. A photosensitive resin laminate according to any one of claims 1 to 4, wherein the content of iron atoms in the photosensitive resin composition layer is 0.4ppm or less based on the photosensitive resin composition layer.

24. A photosensitive resin laminate according to any one of claims 1 to 3, wherein the content of iron atoms in the photosensitive resin composition layer is 0.3ppm or less based on the photosensitive resin composition layer.

25. The photosensitive resin laminate according to claim 1 or 2, wherein the content of iron atoms in the photosensitive resin composition layer is 0.2ppm or less based on the photosensitive resin composition layer.

26. The photosensitive resin laminate according to claim 1, wherein the content of iron atoms in the photosensitive resin composition layer is 0.1ppm or less based on the photosensitive resin composition layer.

27. A photosensitive resin laminate comprising a support film and a photosensitive resin composition layer formed on the support film and containing a photosensitive resin composition,

the photosensitive resin composition contains:

(A) an alkali-soluble polymer;

(B) a compound having an ethylenically unsaturated double bond;

(C) a photopolymerization initiator; and

(E) a calcium atom in the form of a calcium atom,

the content of calcium atoms in the photosensitive resin composition layer is 0.005ppm to 5ppm, based on the photosensitive resin composition layer.

28. The photosensitive resin laminate according to claim 27, wherein a content of calcium atoms in the photosensitive resin composition layer is 0.02ppm or more and 2.5ppm or less, based on the photosensitive resin composition layer.

29. The photosensitive resin laminate according to claim 27, wherein a content of calcium atoms in the photosensitive resin composition layer is 0.03ppm or more and 1ppm or less based on the photosensitive resin composition layer.

30. A photosensitive resin laminate comprising a support film and a photosensitive resin composition layer formed on the support film and containing a photosensitive resin composition,

the photosensitive resin composition contains:

(A) an alkali-soluble polymer;

(B) a compound having an ethylenically unsaturated double bond;

(C) a photopolymerization initiator; and

(F) the aluminum atoms are selected from the group consisting of,

the content of aluminum atoms in the photosensitive resin composition layer is 0.005ppm to 5ppm, based on the photosensitive resin composition layer.

31. The photosensitive resin laminate according to claim 30, wherein a content of aluminum atoms in the photosensitive resin composition layer is 0.02ppm or more and 2.5ppm or less, based on the photosensitive resin composition layer.

32. The photosensitive resin laminate according to claim 30, wherein a content of aluminum atoms in the photosensitive resin composition layer is 0.03ppm or more and 1ppm or less based on the photosensitive resin composition layer.

33. A photosensitive resin laminate comprising a support film and a photosensitive resin composition layer formed on the support film and containing a photosensitive resin composition,

the photosensitive resin composition contains

(A) An alkali-soluble polymer;

(B) a compound having an ethylenically unsaturated double bond;

(C) a photopolymerization initiator;

(D) at least 1 kind of iron atom, calcium atom and aluminum atom,

the total content of iron atoms, calcium atoms and aluminum atoms in the photosensitive resin composition layer is 0.02ppm to 20ppm, based on the photosensitive resin composition layer.

34. The photosensitive resin laminate according to claim 33, wherein the total content of iron atoms, calcium atoms and aluminum atoms in the photosensitive resin composition layer is 0.07ppm or more and 10ppm or less, based on the photosensitive resin composition layer.

35. The photosensitive resin laminate according to claim 33, wherein the total content of iron atoms, calcium atoms and aluminum atoms in the photosensitive resin composition layer is 0.11ppm or more and 5ppm or less, based on the photosensitive resin composition layer.

36. A photosensitive resin laminate comprising a support film and a photosensitive resin composition layer formed on the support film and containing a photosensitive resin composition,

the photosensitive resin composition contains:

(A) an alkali-soluble polymer;

(B) a compound having an ethylenically unsaturated double bond;

(C) a photopolymerization initiator; and

(I) the number of sodium atoms is such that,

the content of sodium atoms in the photosensitive resin composition layer is 1ppm to 50ppm, based on the photosensitive resin composition layer.

37. The photosensitive resin laminate according to claim 36, wherein a content of sodium atoms in the photosensitive resin composition layer is 1.5ppm or more and 25ppm or less based on the photosensitive resin composition layer.

38. The photosensitive resin laminate according to claim 36, wherein a content of sodium atoms in the photosensitive resin composition layer is 2ppm or more and 10ppm or less based on the photosensitive resin composition layer.

39. A photosensitive resin laminate comprising a support film and a photosensitive resin composition layer formed on the support film and containing a photosensitive resin composition,

the photosensitive resin composition contains:

(A) an alkali-soluble polymer;

(B) a compound having an ethylenically unsaturated double bond;

(C) a photopolymerization initiator; and

(J) the metal atom(s) is (are),

the content of the metal atom in the photosensitive resin composition layer is 0.005ppm to 70ppm based on the photosensitive resin composition layer.

40. The photosensitive resin laminate according to claim 39, wherein a content of the metal atom in the photosensitive resin composition layer is 0.01ppm or more and 5ppm or less based on the photosensitive resin composition layer.

41. The photosensitive resin laminate according to claim 39 or 40, wherein the metal atom contains at least one of aluminum, calcium, iron, potassium, magnesium and zinc.

Technical Field

The present invention relates to a photosensitive resin laminate and a method for producing the same.

Background

Printed wiring boards are generally manufactured by photolithography. The photolithography method is a method of forming a desired wiring pattern on a substrate through the following steps. That is, first, a layer containing a photosensitive resin composition is formed on a substrate, and the coating film is pattern-exposed and developed to form a resist pattern. Next, a conductor pattern is formed by etching or plating treatment. Then, the resist pattern on the substrate is removed, thereby forming a desired wiring pattern on the substrate.

In the production of printed wiring boards, photosensitive elements (photosensitive resin laminates) are often used. There are known a plurality of examples of a method for forming a wiring pattern using the photosensitive element and a photosensitive resin composition suitable for the method (patent documents 1 to 3).

Disclosure of Invention

Problems to be solved by the invention

However, the photosensitive resin compositions described in patent documents 1 to 3 do not satisfy the requirements of developing property, adhesion property, and the like at the same time, and there is still room for improvement.

Accordingly, an object of the present invention is to provide a photosensitive resin laminate having a photosensitive resin composition on a base film, which composition can achieve both of developability, which is solubility in a developer, and adhesion to a substrate, particularly a copper substrate, and a method for producing the same.

Means for solving the problems

The present inventors have found that the above problems can be solved by the following technical means.

[1] A photosensitive resin laminate comprising a support film and a photosensitive resin composition layer formed on the support film and containing a photosensitive resin composition,

the photosensitive resin composition contains:

(A) an alkali-soluble polymer;

(B) a compound having an ethylenically unsaturated double bond;

(C) a photopolymerization initiator; and

(D) an iron atom, a nitrogen atom, a fluorine atom,

the content of iron atoms in the photosensitive resin composition layer is 0.01ppm to 10ppm, based on the photosensitive resin composition layer.

[2] The photosensitive resin laminate according to [1], wherein the content of iron atoms in the photosensitive resin composition layer is 0.1ppm or more based on the photosensitive resin composition layer.

[3] The photosensitive resin laminate according to [1], wherein the content of iron atoms in the photosensitive resin composition layer is 0.2ppm or more based on the photosensitive resin composition layer.

[4] The photosensitive resin laminate according to [1], wherein the content of iron atoms in the photosensitive resin composition layer is 0.3ppm or more based on the photosensitive resin composition layer.

[5] The photosensitive resin laminate according to [1], wherein the content of iron atoms in the photosensitive resin composition layer is 0.4ppm or more based on the photosensitive resin composition layer.

[6] The photosensitive resin laminate according to [1], wherein the content of iron atoms in the photosensitive resin composition layer is 0.5ppm or more based on the photosensitive resin composition layer.

[7] The photosensitive resin laminate according to [1], wherein the content of iron atoms in the photosensitive resin composition layer is 0.6ppm or more based on the photosensitive resin composition layer.

[8] The photosensitive resin laminate according to [1], wherein the content of iron atoms in the photosensitive resin composition layer is 0.7ppm or more based on the photosensitive resin composition layer.

[9] The photosensitive resin laminate according to [1], wherein the content of iron atoms in the photosensitive resin composition layer is 0.8ppm or more based on the photosensitive resin composition layer.

[10] The photosensitive resin laminate according to [1], wherein the content of iron atoms in the photosensitive resin composition layer is 0.9ppm or more based on the photosensitive resin composition layer.

[11] The photosensitive resin laminate according to [1], wherein the content of iron atoms in the photosensitive resin composition layer is 1.0ppm or more based on the photosensitive resin composition layer.

[12] The photosensitive resin laminate according to [1], wherein the content of iron atoms in the photosensitive resin composition layer is 2.0ppm or more based on the photosensitive resin composition layer.

[13] The photosensitive resin laminate according to [1], wherein the content of iron atoms in the photosensitive resin composition layer is 3.0ppm or more based on the photosensitive resin composition layer.

[14] The photosensitive resin laminate according to any one of [1] to [13], wherein the content of iron atoms in the photosensitive resin composition layer is 5.0ppm or less based on the photosensitive resin composition layer.

[15] The photosensitive resin laminate according to any one of [1] to [11], wherein the content of iron atoms in the photosensitive resin composition layer is 2.0ppm or less based on the photosensitive resin composition layer.

[16] The photosensitive resin laminate according to any one of [1] to [11], wherein the content of iron atoms in the photosensitive resin composition layer is 1.5ppm or less based on the photosensitive resin composition layer.

[17] The photosensitive resin laminate according to any one of [1] to [10], wherein the content of iron atoms in the photosensitive resin composition layer is 1.0ppm or less based on the photosensitive resin composition layer.

[18] The photosensitive resin laminate according to any one of [1] to [9], wherein the content of iron atoms in the photosensitive resin composition layer is 0.9ppm or less based on the photosensitive resin composition layer.

[19] The photosensitive resin laminate according to any one of [1] to [8], wherein the content of iron atoms in the photosensitive resin composition layer is 0.8ppm or less based on the photosensitive resin composition layer.

[20] The photosensitive resin laminate according to any one of [1] to [7], wherein the content of iron atoms in the photosensitive resin composition layer is 0.7ppm or less based on the photosensitive resin composition layer.

[21] The photosensitive resin laminate according to any one of [1] to [6], wherein the content of iron atoms in the photosensitive resin composition layer is 0.6ppm or less based on the photosensitive resin composition layer.

[22] The photosensitive resin laminate according to any one of [1] to [5], wherein the content of iron atoms in the photosensitive resin composition layer is 0.5ppm or less based on the photosensitive resin composition layer.

[23] The photosensitive resin laminate according to any one of [1] to [4], wherein the content of iron atoms in the photosensitive resin composition layer is 0.4ppm or less based on the photosensitive resin composition layer.

[24] The photosensitive resin laminate according to any one of [1] to [3], wherein the content of iron atoms in the photosensitive resin composition layer is 0.3ppm or less based on the photosensitive resin composition layer.

[25] The photosensitive resin laminate according to [1] or [2], wherein the content of iron atoms in the photosensitive resin composition layer is 0.2ppm or less based on the photosensitive resin composition layer.

[26] The photosensitive resin laminate according to [1], wherein the content of iron atoms in the photosensitive resin composition layer is 0.1ppm or less based on the photosensitive resin composition layer.

[27] A photosensitive resin laminate comprising a support film and a photosensitive resin composition layer formed on the support film and containing a photosensitive resin composition,

the photosensitive resin composition contains:

(A) an alkali-soluble polymer;

(B) a compound having an ethylenically unsaturated double bond;

(C) a photopolymerization initiator; and

(E) a calcium atom in the form of a calcium atom,

the content of calcium atoms in the photosensitive resin composition layer is 0.005ppm to 5ppm, based on the photosensitive resin composition layer.

[28] The photosensitive resin laminate according to [27], wherein the content of calcium atoms in the photosensitive resin composition layer is 0.02ppm to 2.5ppm, based on the photosensitive resin composition layer.

[29] The photosensitive resin laminate according to [27], wherein the content of calcium atoms in the photosensitive resin composition layer is 0.03ppm to 1ppm, based on the photosensitive resin composition layer.

[30] A photosensitive resin laminate comprising a support film and a photosensitive resin composition layer formed on the support film and containing a photosensitive resin composition,

the photosensitive resin composition contains:

(A) an alkali-soluble polymer;

(B) a compound having an ethylenically unsaturated double bond;

(C) a photopolymerization initiator; and

(F) the aluminum atoms are selected from the group consisting of,

the content of aluminum atoms in the photosensitive resin composition layer is 0.005ppm to 5ppm, based on the photosensitive resin composition layer.

[31] The photosensitive resin laminate according to [30], wherein the content of aluminum atoms in the photosensitive resin composition layer is 0.02ppm to 2.5ppm, based on the photosensitive resin composition layer.

[32] The photosensitive resin laminate according to [30], wherein the content of aluminum atoms in the photosensitive resin composition layer is 0.03ppm to 1ppm, based on the photosensitive resin composition layer.

[33] A photosensitive resin laminate comprising a support film and a photosensitive resin composition layer formed on the support film and containing a photosensitive resin composition,

the photosensitive resin composition contains:

(A) an alkali-soluble polymer;

(B) a compound having an ethylenically unsaturated double bond;

(C) a photopolymerization initiator;

(D) at least 1 kind of iron atom, calcium atom and aluminum atom,

the total content of iron atoms, calcium atoms and aluminum atoms in the photosensitive resin composition layer is 0.02ppm to 20ppm based on the photosensitive resin composition layer.

[34] The photosensitive resin laminate according to [33], wherein the total content of iron atoms, calcium atoms, and aluminum atoms in the photosensitive resin composition layer is 0.07ppm or more and 10ppm or less, based on the photosensitive resin composition layer.

[35] The photosensitive resin laminate according to [33], wherein the total content of iron atoms, calcium atoms, and aluminum atoms in the photosensitive resin composition layer is 0.11ppm or more and 5ppm or less, based on the photosensitive resin composition layer.

[36] A photosensitive resin laminate comprising a support film and a photosensitive resin composition layer formed on the support film and containing a photosensitive resin composition,

the photosensitive resin composition contains:

(A) an alkali-soluble polymer;

(B) a compound having an ethylenically unsaturated double bond;

(C) a photopolymerization initiator; and

(I) the number of sodium atoms is such that,

the content of sodium atoms in the photosensitive resin composition layer is 1ppm to 50ppm, based on the photosensitive resin composition layer.

[37] The photosensitive resin laminate according to [36], wherein the content of sodium atoms in the photosensitive resin composition layer is 1.5ppm or more and 25ppm or less based on the photosensitive resin composition layer.

[38] The photosensitive resin laminate according to [36], wherein the content of sodium atoms in the photosensitive resin composition layer is 2ppm to 10ppm, based on the photosensitive resin composition layer.

[39] A photosensitive resin laminate comprising a support film and a photosensitive resin composition layer formed on the support film and containing a photosensitive resin composition,

the photosensitive resin composition contains:

(A) an alkali-soluble polymer;

(B) a compound having an ethylenically unsaturated double bond;

(C) a photopolymerization initiator; and

(J) the metal atom(s) is (are),

the content of the metal atom in the photosensitive resin composition layer is 0.005ppm to 70ppm based on the photosensitive resin composition layer.

[40] The photosensitive resin laminate according to [39], wherein a content of the metal atom in the photosensitive resin composition layer is 0.01ppm or more and 5ppm or less based on the photosensitive resin composition layer.

[41] The photosensitive resin laminate according to [39] or [40], wherein the metal atom contains at least one of aluminum, calcium, iron, potassium, magnesium, and zinc.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a laminate comprising a photosensitive resin composition on a base film, which composition can achieve both of developability, which is solubility in a developer, and adhesion to a substrate, particularly a copper substrate, is provided, whereby the resolution of a printed wiring board formed using a dry film resist can be improved.

Detailed Description

Hereinafter, a mode for carrying out the present invention (hereinafter, simply referred to as "the present embodiment") will be specifically described.

In the present specification, the term "(meth) acrylic acid" refers to acrylic acid or methacrylic acid. The term "(meth) acryl" refers to acryl or methacryl. The term "(meth) acrylate" refers to either "acrylate" or "methacrylate".

< photosensitive resin composition >

The embodiment is a photosensitive resin laminate comprising a support film and a photosensitive resin composition layer formed on the support film and containing a photosensitive resin composition,

the photosensitive resin composition comprises (A) an alkali-soluble polymer, (B) an ethylenically unsaturated bond-containing compound, (C) a photopolymerization initiator, and (J) a metal atom. (J) The metal atom includes (D) an iron atom, (E) a calcium atom, and (F) at least 1 of an aluminum atom and zinc. The metal atom (J) may include a sodium atom (I). The photosensitive resin composition may further contain other components such as (G) a photosensitizer and (H) an additive, as desired.

In particular, in the present embodiment, the content of the metal atom (J) in the photosensitive resin composition layer is 0.005ppm or more and 70ppm or less, preferably 0.01ppm or more and 5ppm or less, based on the photosensitive resin composition layer. Specifically, the content of (D) iron atoms is 0.01ppm to 10ppm based on the photosensitive resin composition layer. Alternatively, the content of any one of (E) calcium atoms and (F) aluminum atoms is 0.005ppm to 5ppm based on the photosensitive resin composition layer. Alternatively, the content of (I) sodium atoms is 1ppm to 50ppm based on the photosensitive resin composition layer.

When the content of the metal atom, for example, iron atom, calcium atom, aluminum atom, or sodium atom is in the above range, the solubility in the developer, that is, the developability and the adhesion to the substrate, particularly, a copper substrate can be both satisfied. By improving the developability, the resist pattern is less likely to leave residues, and by improving the adhesion to the substrate, a finer resist pattern can be formed.

The respective components will be explained in turn below.

(A) Alkali soluble polymer

(A) The alkali-soluble polymer is a polymer that is soluble in an alkali substance. (A) The alkali soluble polymer may be a single copolymer, a mixture of copolymers, and/or a mixture of homopolymers.

The alkali solubility is preferably 100 or more in terms of the development resistance of the photosensitive resin composition layer, and the development resistance, resolution, and adhesion of the resist pattern, and the acid equivalent of the (a) alkali-soluble polymer (in the case where the (a) component includes a plurality of copolymers, the acid equivalent of the entire mixture thereof). From the viewpoint of developability and releasability of the photosensitive resin composition layer, it is preferably 900 or less. (A) The alkali-soluble polymer preferably has an acid equivalent of 200 to 600, more preferably 250 to 500. The acid equivalent is: mass of the linear polymer having 1 equivalent of carboxyl group therein.

(A) Alkali soluble polymer

(A) The alkali-soluble polymer is a polymer which is easily soluble in an alkali substance. Specifically, the polymer is a polymer having a functional group (e.g., a carboxyl group) contributing to alkali solubility in an amount sufficient to dissolve in a desired alkali substance. Typically, the amount of carboxyl groups contained in the alkali-soluble polymer (A) is 100 to 600, preferably 250 to 450 in terms of acid equivalent. The acid equivalent is: the mass (unit: g) of the linear polymer having 1 equivalent of carboxyl group in its molecule. (A) The carboxyl group in the alkali-soluble polymer is necessary to impart developability and releasability to the photosensitive resin composition layer with an alkali aqueous solution. From the viewpoint of improving the development resistance, resolution, and adhesion, the acid equivalent is preferably 100 or more, and the acid equivalent is preferably 250 or more. On the other hand, from the viewpoint of improving the developability and the peelability, the acid equivalent is preferably 600 or less, and the acid equivalent is preferably 450 or less.

(A) The weight average molecular weight of the alkali-soluble polymer is preferably 5,000 to 500,000. From the viewpoint of improving resolution and developability, the weight average molecular weight is preferably 500,000 or less. The weight average molecular weight is more preferably 300,000 or less, and still more preferably 200,000 or less. On the other hand, from the viewpoint of controlling the properties of development aggregates and the properties of an unexposed film such as the edge fusibility and the chipping property of the photosensitive resin laminate, the weight average molecular weight is preferably 5,000 or more. The weight average molecular weight is more preferably 10,000 or more, and still more preferably 20,000 or more. The edge fusibility means that: when the photosensitive resin laminate is wound into a roll shape, the photosensitive resin composition layer protrudes from an end face of the roll. The swarf property is: a phenomenon that chips are scattered when an unexposed film is cut by a knife. If the debris adheres to the upper surface of the photosensitive resin laminate, the debris is transferred to the mask in a subsequent exposure step or the like, which causes defective products.

(A) The dispersion degree (also referred to as molecular weight distribution) of the alkali-soluble polymer may be about 1 to 6, preferably 1 to 4. The degree of dispersion is expressed as the ratio of the weight average molecular weight to the number average molecular weight, and (degree of dispersion) — the (weight average molecular weight)/(number average molecular weight). The weight average molecular weight and the number average molecular weight are values measured by gel permeation chromatography in terms of polystyrene.

(A) The alkali-soluble polymer is preferably a copolymer obtained from at least 1 kind of first monomer described later and at least 1 kind of second monomer described later.

The first monomer is a carboxylic acid or an acid anhydride having 1 polymerizable unsaturated group in the molecule. Examples of the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid half ester. Particularly preferred is (meth) acrylic acid. In the present specification, (meth) acrylic acid means acrylic acid and/or methacrylic acid. The same applies below.

The second monomer is a non-acidic monomer having at least 1 polymerizable unsaturated group in the molecule. Examples of the second monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, and esters of vinyl alcohol. Examples of the esters of vinyl alcohol include vinyl acetate, (meth) acrylonitrile, styrene, and styrene derivatives. Among them, methyl (meth) acrylate, n-butyl (meth) acrylate, styrene, 2-ethylhexyl (meth) acrylate, and benzyl (meth) acrylate are preferable. Styrene and benzyl (meth) acrylate are preferable from the viewpoint of improving the resolution and adhesion of the resist pattern.

From the viewpoint of adjusting the alkali solubility of the alkali-soluble polymer (a), the copolymerization ratio of the first monomer and the second monomer is preferably 10 to 60 mass% for the first monomer and 40 to 90 mass% for the second monomer. More preferably, the amount of the first monomer is 15 to 35% by mass and the amount of the second monomer is 65 to 85% by mass.

It is preferable to synthesize (a) an alkali-soluble polymer by adding an appropriate amount of a radical polymerization initiator such as benzoyl peroxide or azoisobutyronitrile to a solution obtained by diluting a mixture of a first monomer and a second monomer with a solvent such as acetone, methyl ethyl ketone, or isopropyl alcohol, and heating and stirring the mixture. The synthesis may be performed while a part of the mixture is added dropwise to the reaction solution. After the completion of the reaction, a solvent may be further added to adjust the concentration to a desired level. As a synthesis means, in addition to solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization may be used.

The ratio of the alkali-soluble polymer (a mixture thereof in the case of using a plurality of alkali-soluble polymers in a mixture) to the total amount of the components (a), (B), (C), (D), (G), (H), and (I) and (J) (hereinafter, may be referred to as the total amount of the components (a) to (J)) is preferably in the range of 10 to 90 mass%, more preferably 30 to 70 mass%, and still more preferably 40 to 60 mass%. From the viewpoint of controlling the development time, the proportion of the component (a) to the total amount of the components (a) to (J) is preferably 90 mass% or less. On the other hand, from the viewpoint of improving the marginal fusion property, the proportion of the component (a) to the total amount of the components (a) to (J) is preferably 10% by mass or more.

Particularly, from the viewpoint of exhibiting high resolution, it is preferable that the photosensitive resin composition contains 1 or more components selected from the group consisting of the following (a-1) and (a-2) as the (a) component:

(a-1) an acrylic copolymer derived from a polymerization component comprising 15 to 60 mass% of styrene and 1 or more acrylic monomers selected from the group consisting of acrylic acid, methacrylic acid, acrylic acid esters and methacrylic acid esters;

(a-2) an acrylic copolymer derived from a polymerization component comprising benzyl methacrylate in an amount of 20 to 85 mass% and 1 or more acrylic monomers selected from the group consisting of acrylic acid, methacrylic acid, acrylic acid esters and methacrylic acid esters other than benzyl methacrylate.

The ratio of the total amount of the component (a-1) and the component (a-2) to the total amount of the components (A) to (J) is preferably 10 to 60% by mass in terms of expression of high resolution. The above proportion is preferably 20 mass% or more, more preferably 30 mass% or more from the viewpoint of resolution, and is preferably 55 mass% or less, more preferably 50 mass% or less from the viewpoint of cutting property.

The polymerization component in (a-1) may contain only styrene and the above-mentioned acrylic monomer, or may further contain another monomer. The polymerizable component in (a-2) may contain only benzyl methacrylate and the acrylic monomer, or may further contain another monomer. Particularly preferred examples of the combination of the polymerization components include: a combination of 15 to 60% by mass of styrene, 20 to 35% by mass of methacrylic acid, and the balance methyl methacrylate; 30 to 50% by mass of styrene, 20 to 40% by mass of methacrylic acid, 10 to 20% by mass of 2-ethylhexyl acrylate, and the balance of 2-hydroxyethyl methacrylate; or a combination of 20 to 60 mass% of benzyl methacrylate, 10 to 30 mass% of styrene, and the balance methacrylic acid; a combination of 60 to 85 mass% of benzyl methacrylate, 0 to 15 mass% of 2-ethylhexyl acrylate, and the balance methacrylic acid; and the like. From the viewpoint of chemical resistance, adhesion, high resolution, or sag shape of the resist pattern, it is preferable to contain a monomer having an aralkyl group and/or styrene as a monomer.

(B) Compounds having ethylenically unsaturated double bonds

(B) The ethylenically unsaturated bond-containing compound is a compound having an ethylenically unsaturated group in its structure and thus having polymerizability. The ethylenically unsaturated bond is preferably a terminal ethylenically unsaturated group from the viewpoint of addition polymerizability.

The compound (B) having an ethylenically unsaturated double bond preferably includes a compound having an acryloyl group in the molecule from the viewpoint of curability and compatibility with the alkali-soluble polymer (a). Examples of the compound having an acryloyl group in the molecule include a compound in which (meth) acrylic acid is added to one end of a polyalkylene oxide, a compound in which (meth) acrylic acid is added to one end of a polyalkylene oxide and the other end is subjected to alkyl etherification or allyl etherification, and the like.

Examples of such compounds include: phenoxy hexaethylene glycol mono (meth) acrylate as a (meth) acrylate of a compound in which polyethylene glycol is added to a phenyl group; or 4-n-nonylphenoxy heptaethyleneglycol dipropylene glycol (meth) acrylate which is a (meth) acrylate of a compound obtained by adding to nonylphenol a polypropylene glycol obtained by adding an average of 2 moles of propylene oxide (hereinafter also referred to simply as PO) and a polyethylene glycol obtained by adding an average of 7 moles of ethylene oxide (hereinafter also referred to simply as EO); 4-n-nonylphenoxypentaethylene glycol monopropylene glycol (meth) acrylate which is a (meth) acrylate of a compound obtained by adding polypropylene glycol obtained by adding 1 mole of propylene oxide on the average and polyethylene glycol obtained by adding 5 moles of ethylene oxide on the average to nonylphenol. Further, 4-n-nonylphenoxy octaethylene glycol (meth) acrylate (for example, M-114, manufactured by Toyo Seiya Kabushiki Kaisha) which is an acrylate of a compound obtained by adding polyethylene glycol obtained by adding an average of 8 moles of ethylene oxide to nonylphenol is also included.

Examples thereof include: a compound having a (meth) acryloyl group at both ends of an oxyalkylene chain; or a compound having a (meth) acryloyl group at each end of an oxyalkylene chain in which an oxyethylene chain and an oxypropylene chain are randomly or blockwise bonded.

Examples of such compounds include polyethylene glycol (meth) acrylates such as tetraethylene glycol di (meth) acrylate, pentaethylene glycol di (meth) acrylate, hexaethylene glycol di (meth) acrylate, heptaethylene glycol di (meth) acrylate, octaethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, decaethylene glycol di (meth) acrylate, and compounds having (meth) acryloyl groups at both ends of a 12-mole oxyethylene chain, polypropylene glycol di (meth) acrylate, and polybutylene glycol di (meth) acrylate. As the polyalkylene oxide di (meth) acrylate compound containing an oxyethylene group and an oxypropylene group in the compound, for example, there can be mentioned: a glycol dimethacrylate obtained by adding an average of 3 moles of ethylene oxide to each of both ends of a polypropylene glycol obtained by adding an average of 12 moles of propylene oxide, a glycol dimethacrylate obtained by adding an average of 15 moles of ethylene oxide to each of both ends of a polypropylene glycol obtained by adding an average of 18 moles of propylene oxide, and the like. Further, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and di (meth) acrylate having both ethylene oxide and polypropylene oxide are preferable from the viewpoints of flexibility, resolution, adhesiveness, and the like (for example, "FA-023M, FA-024M, FA-027M, product name, hitachi chemical industry product").

In addition, from the viewpoint of resolution and adhesion, a compound in which bisphenol a is modified with an alkylene oxide and has (meth) acryloyl groups at both ends is preferable. As the alkylene oxide modification, ethylene oxide modification, propylene oxide modification, butylene oxide modification, pentylene oxide modification, hexylene oxide modification, and the like are given. In addition, from the viewpoint of resolution and adhesion, a compound in which bisphenol a is ethylene oxide-modified and has (meth) acryloyl groups at both ends is particularly preferable.

Examples of such compounds include: 2, 2-bis (4- ((meth) acryloyloxydiethoxy) phenyl) propane (e.g., NK ESTER BPE-200 manufactured by Newzhou chemical Co., Ltd.), 2-bis (4- ((meth) acryloyloxytetraethoxy) phenyl) propane, 2-bis (4- ((meth) acryloyloxypentaethoxy) phenyl) propane (e.g., NK ESTer BPE-500 manufactured by Newzhou chemical Co., Ltd.), 2-bis (4- ((meth) acryloyloxyhexaethoxy) phenyl) propane, 2-bis (4- ((meth) acryloyloxyheptaethoxy) phenyl) propane, 2-bis (4- ((meth) acryloyloxyoctaethoxy) phenyl) propane, 2 such as 2, 2-bis (4- ((meth) acryloyloxynonoethoxyphenyl) propane, 2-bis (4- ((meth) acryloyloxydodecoxyethyl) phenyl) propane, 2-bis (4- ((meth) acryloyloxydecylethyl) phenyl) propane, 2-bis (4- ((meth) acryloyloxydodecoxyethyl) phenyl) propane, 2-bis (4- ((meth) acryloyloxytridecyloxyethyl) phenyl) propane, 2-bis (4- ((meth) acryloyloxytetradecythoxy) phenyl) propane, 2-bis (4- ((meth) acryloyloxypentadecaethoxy) phenyl) propane, 2-bis (4- ((meth) acryloyloxydechexadecylethoxy) phenyl) propane and the like, 2-bis (4- ((meth) acryloyloxypolyethoxy) phenyl) propane, and the like. Further, from the viewpoint of resolution and adhesion, ethylene oxide-modified and propylene oxide-modified compounds such as a di (meth) acrylate of a polyalkylene glycol obtained by adding an average of 2 moles of propylene oxide and an average of 6 moles of ethylene oxide to both ends of bisphenol a, a di (meth) acrylate of a polyalkylene glycol obtained by adding an average of 2 moles of propylene oxide and an average of 15 moles of ethylene oxide to both ends of bisphenol a, and a dimethacrylate of a polyethylene glycol obtained by adding an average of 5 moles of EO to both ends of bisphenol a (for example, BPE-500 manufactured by shinkamura chemical corporation) are also preferable. In the compounds obtained by modifying bisphenol a with an alkylene oxide and having (meth) acryloyl groups at both ends thereof, the total number of moles of ethylene oxide per 1 mole of bisphenol a is preferably 10 to 30 moles in view of improving resolution, adhesion, and flexibility.

In the present embodiment, from the viewpoint of exhibiting high resolution, it is preferable to include a compound having more than 2 (meth) acryloyl groups in one molecule as (B) the compound having an ethylenically unsaturated double bond. The number of (meth) acryloyl groups in one molecule is more preferably 3 or more. From the viewpoint of peelability, the number of (meth) acryloyl groups in one molecule is preferably 6 or less, and more preferably 4 or less. Compounds having more than 2 (meth) acryloyl groups in one molecule are obtainable as follows: the (meth) acrylate is obtained by forming a (meth) acrylate from (meth) acrylic acid and an alcohol having, as a central skeleton, 3 moles or more of groups capable of adding an alkylene oxide group (i.e., 3 or more with respect to 1 central skeleton) in a molecule and having an alkylene oxide group such as an ethylene oxide group, a propylene oxide group, or a butylene oxide group added thereto. When the central skeleton is an alcohol, it can also be obtained by directly forming a (meth) acrylate with (meth) acrylic acid. Examples of the compound that can be a central skeleton include glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, and isocyanurate rings.

Examples of such a compound include a trimethylolpropane EO 3 mol-modified triacrylate, trimethylolpropane EO 6 mol-modified triacrylate, trimethylolpropane EO 9 mol-modified triacrylate, trimethylolpropane EO 12 mol-modified triacrylate, glycerol EO 3 mol-modified triacrylate (for example, A-GLY-3E manufactured by Nippon Korea chemical Co., Ltd.), glycerol EO 9 mol-modified triacrylate (for example, A-GLY-9E manufactured by Nippon Korea chemical Co., Ltd.), glycerol EO 6 mol, PO 6 mol-modified triacrylate (A-GLY-0606PE), glycerol EO 9 mol, PO9 mol-modified triacrylate (A-GLY-0909PE), pentaerythritol 4 EO-modified tetraacrylate (for example, SR-494 manufactured by サートマージャパン Co., Ltd.), Pentaerythritol 35 EO-modified tetraacrylate (for example, NK ESTER ATM-35E manufactured by shinkamura chemical industry, ltd.), dipentaerythritol tetraacrylate, pentaerythritol triacrylate, and pentaerythritol tetraacrylate 7: 3 mixture (for example, M-306, manufactured by Toyo Seiya K.K.), etc. In addition, as the compound having at least 3 methacryloyl groups, there can be mentioned: trimethacrylates such as ethoxylated glycerol trimethacrylate, ethoxylated isocyanuric acid trimethacrylate, pentaerythritol trimethacrylate, trimethylolpropane trimethacrylate (for example, trimethacrylate in which 21 moles of ethylene oxide on average is added to trimethylolpropane and trimethacrylate in which 30 moles of ethylene oxide on average is added to trimethylolpropane are preferable from the viewpoints of flexibility, adhesion, and bleeding inhibition); tetramethylacrylates such as ditrimethylolpropane tetramethylacrylate, pentaerythritol tetramethylacrylate, dipentaerythritol tetramethylacrylate, and the like; pentamethyl acrylates such as dipentaerythritol pentamethyl acrylate and the like; hexamethylacrylate such as dipentaerythritol hexamethacrylate and the like. Among these, tetramethylacrylate, pentamethylacrylate, or hexamethylacrylate is preferable.

Among these, preferred examples of the compound (B) having an ethylenically unsaturated double bond are those having a melting point lower than room temperature and not easily cured during storage, from the viewpoint of handling properties. Particularly preferred are trimethylolpropane EO 3 mol-modified triacrylate and pentaerythritol 4 EO-modified tetraacrylate.

The content of the compound having more than 2 (meth) acryloyl groups in one molecule is preferably 50 to 100% by mass of the compound having an ethylenically unsaturated double bond (B). From the viewpoint of resolution, the content is preferably 50% by mass or more, and more preferably 60% by mass or more. The content may be 100 mass%, but from the viewpoint of peelability, it may be preferably 95 mass% or less, more preferably 90 mass% or less.

The component (B) may suitably contain, in addition to the above-mentioned compounds, for example, the compounds listed below. Examples thereof include: 1, 6-hexanediol di (meth) acrylate, 1, 4-cyclohexanediol di (meth) acrylate, 2-bis (p-hydroxyphenyl) propane di (meth) acrylate, 2-bis [ (4- (meth) acryloyloxypolyoxypropylene) phenyl ] propane, 2-bis [ (4- (meth) acryloyloxypolyoxybutylene) phenyl ] propane, glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyoxypropyltrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane triglycidyl ether tri (meth) acrylate, beta-hydroxypropyl-beta' - (acryloyloxy) propyl phthalate, nonylphenoxypolypropylene glycol (meth) acrylate, and mixtures thereof, Nonylphenoxy polytetramethylene glycol (meth) acrylate, polypropylene glycol mono (meth) acrylate, and the like. Further, the following urethane compounds can be also exemplified. Examples thereof include: hexamethylene diisocyanate, toluene diisocyanate, or a diisocyanate compound (e.g., 2, 4-trimethylhexamethylene diisocyanate) with a compound having a hydroxyl group and a (meth) acryloyl group in one molecule, such as 2-hydroxypropyl acrylate, urethane compounds of oligomeric propylene glycol monomethacrylate. Specifically, there is a reaction product of hexamethylene diisocyanate and an oligo-propylene glycol monomethacrylate (for example, BLEMMER PP1000 manufactured by nippon fat & oil corporation). Further, di-or tri (meth) acrylate of isocyanurate modified with polypropylene glycol or polycaprolactone, and the like are also included. Further, there may be mentioned, for example: urethane oligomers obtained by reacting the terminal of a urethane compound obtained as an addition polymer of a diisocyanate and a polyol with a compound having an ethylenically unsaturated double bond and a hydroxyl group, and the like.

The compound (B) having an ethylenically unsaturated bond may also contain a compound having 1 ethylenically unsaturated bond such as 4-n-nonylphenoxy octaethyleneglycol acrylate, 4-n-nonylphenoxy tetraethylene glycol acrylate, or γ -chloro- β -hydroxypropyl- β' -methacryloyloxyethyl phthalate. The composition is preferable from the viewpoint of releasability and cured film flexibility, and the composition containing γ -chloro- β -hydroxypropyl- β' -methacryloyloxyethyl phthalate is also preferable from the viewpoint of sensitivity, resolution and adhesiveness.

The above-mentioned (B) compound having an ethylenically unsaturated double bond preferably contains a hydroxyl group in the molecule. Therefore, the sensitivity (productivity), resolution, and adhesion are particularly excellent.

(B) The proportion of the compound having an ethylenically unsaturated double bond to the total amount of the components (A) to (J) is preferably 5 to 70% by mass. From the viewpoint of sensitivity, resolution, and adhesion, the ratio is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 20% by mass or more. On the other hand, from the viewpoint of suppressing edge fusion and peeling delay of the cured resist, the ratio is preferably 70% by mass or less, more preferably 60% by mass or less, and still more preferably 50% by mass or less.

(C) Photopolymerization initiator

From the viewpoint of obtaining sensitivity and resolution, the (C) photopolymerization initiator preferably contains a hexaarylbiimidazole compound.

Examples of the hexaarylbiimidazole compound include 2- (o-chlorophenyl) -4, 5-diphenylbiimidazole, 2 ', 5-tris (o-chlorophenyl) -4- (3, 4-dimethoxyphenyl) -4', 5 '-diphenylbiimidazole, 2, 4-bis- (o-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -diphenylbiimidazole, 2,4, 5-tris (o-chlorophenyl) -diphenylbiimidazole, 2- (o-chlorophenyl) -bis-4, 5- (3, 4-dimethoxyphenyl) -biimidazole, 2' -bis- (2-fluorophenyl) -4,4 ', 5, 5' -tetrakis- (3-methoxyphenyl) -biimidazole, and mixtures thereof, 2,2 ' -bis- (2, 3-difluoromethylphenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -biimidazole, 2 ' -bis- (2, 4-difluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -biimidazole, 2 ' -bis- (2, 5-difluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -biimidazole, 2 ' -bis- (2, 6-difluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -biimidazole, 2 ' -bis- (2,3, 4-trifluorophenyl) -4,4 ', 5, 5' -tetrakis- (3-methoxyphenyl) -biimidazole, 2 '-bis- (2,3, 5-trifluorophenyl) -4, 4', 5,5 '-tetrakis- (3-methoxyphenyl) -biimidazole, 2' -bis- (2,3, 6-trifluorophenyl) -4,4 ', 5, 5' -tetrakis- (3-methoxyphenyl) -biimidazole, 2 '-bis- (2,4, 5-trifluorophenyl) -4, 4', 5,5 '-tetrakis- (3-methoxyphenyl) -biimidazole, 2' -bis- (2,4, 6-trifluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -biimidazole, 2 ' -bis- (2,3,4, 5-tetrafluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -biimidazole, 2 ' -bis- (2,3,4, 6-tetrafluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -biimidazole, and 2,2 ' -bis- (2,3,4,5, 6-pentafluorophenyl) -4,4 ', 5,5 ' -tetrakis- (3-methoxyphenyl) -biimidazole, and the like. Among them, 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer is preferable from the viewpoint of sensitivity and resolution.

Examples of the photopolymerization initiator other than the hexaarylbiimidazole compound, which may be contained as component (C), include N-aryl- α -amino acid compounds, quinones, aromatic ketones, acetophenones, acylphosphine oxides, benzoin or benzoin ethers, dialkyl ketals, thioxanthones, dialkyl aminobenzoate esters, oxime esters, acridines, ester compounds of N-aryl amino acids, and halogen compounds.

Examples of the N-aryl- α -amino acid compound include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine and the like. Particularly, N-phenylglycine is preferable because of its high sensitizing effect.

Examples of the quinones include 2-ethylanthraquinone, octaethylanthraquinone, 1, 2-benzoanthraquinone, 2, 3-benzoanthraquinone, 2-phenylanthraquinone, 2, 3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1, 4-naphthoquinone, 9, 10-phenanthrenequinone, 2-methyl-1, 4-naphthoquinone, 2, 3-dimethylanthraquinone, and 3-chloro-2-methylanthraquinone.

Examples of the aromatic ketone include benzophenone, michler's ketone [4, 4' -bis (dimethylamino) benzophenone ], 4 '-bis (diethylamino) benzophenone, and 4-methoxy-4' -dimethylamino benzophenone.

Examples of the acetophenone include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) one, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, and 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-acetone-1. Examples of commercially available products include Irgacure907, Irgacure369 and Irgacure379 available from Ciba Specialty Chemicals.

Examples of acylphosphine oxides include 2,4, 6-trimethylbenzyldiphenylphosphine oxide, bis (2,4, 6-trimethylbenzoyl) -phosphine oxide, bis (2, 6-dimethoxybenzoyl) -2,4, 4-trimethyl-pentylphosphine oxide, and the like. Commercially available products include Lucirin TPO manufactured by BASF corporation and Irgacure819 manufactured by Ciba Specialty Chemicals corporation.

Examples of benzoin and benzoin ethers include benzoin, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, and ethyl benzoin.

As the dialkyl ketal, benzil dimethyl ketal and benzil diethyl ketal can be mentioned, for example.

Examples of the thioxanthones include 2, 4-diethylthioxanthone, 2, 4-diisopropylthioxanthone, and 2-chlorothioxanthone.

Examples of the dialkylaminobenzoate include ethyl dimethylaminobenzoate, ethyl diethylaminobenzoate, ethyl p-dimethylaminobenzoate, and 2-ethylhexyl 4- (dimethylamino) benzoate.

Examples of the oxime esters include 1-phenyl-1, 2-propanedione-2-O-benzoyl oxime and 1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) oxime. Commercially available products include CGI-325, Irgacure OXE01 and Irgacure OXE02 available from Ciba Specialty Chemicals.

Examples of the acridines include 1, 7-bis (9, 9' -acridinyl) heptane, 9-phenylacridine, 9-methylacridine, 9-ethylacridine, 9-chloroethylacridine, 9-methoxyacridine, 9-ethoxyacridine, 9- (4-methylphenyl) acridine, 9- (4-ethylphenyl) acridine, 9- (4-n-propylphenyl) acridine, 9- (4-n-butylphenyl) acridine, 9- (4-tert-butylphenyl) acridine, 9- (4-methoxyphenyl) acridine, 9- (4-ethoxyphenyl) acridine, 9- (4-acetylphenyl) acridine, 9- (4-dimethylaminophenyl) acridine, 9- (4-chlorophenyl) acridine, 9-methylacridine, and the like, 9- (4-bromophenyl) acridine, 9- (3-methylphenyl) acridine, 9- (3-tert-butylphenyl) acridine, 9- (3-acetylphenyl) acridine, 9- (3-dimethylaminophenyl) acridine, 9- (3-diethylaminophenyl) acridine, 9- (3-chlorophenyl) acridine, 9- (3-bromophenyl) acridine, 9- (2-pyridyl) acridine, 9- (3-pyridyl) acridine, and 9- (4-pyridyl) acridine.

Examples of the ester compound of an N-arylamino acid include methyl ester of N-phenylglycine, ethyl ester of N-phenylglycine, N-propyl ester of N-phenylglycine, isopropyl ester of N-phenylglycine, 1-butyl ester of N-phenylglycine, 2-butyl ester of N-phenylglycine, t-butyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, hexyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, and octyl ester of N-phenylglycine.

Examples of the halogen compound include amyl bromide, isoamyl bromide, bromoisobutylene, vinyl bromide, diphenylmethyl bromide, benzyl bromide, dibromomethane, tribromomethylphenylsulfone, carbon tetrabromide, tris (2, 3-dibromopropyl phosphate), trichloroacetamide, amyl iodide, isobutyl iodide, 1,1, 1-trichloro-2, 2-bis (p-chlorophenyl) ethane, a triazine chloride compound, and a diallyl iodonium compound, and tribromomethylphenylsulfone is particularly preferable. The content of the halogen compound in the photosensitive resin composition is preferably 0.01 to 3% by mass relative to the total amount of the components (a) to (J) from the viewpoint of sensitivity.

These photopolymerization initiators may be used alone or in combination of two or more.

(C) The proportion of the photopolymerization initiator to the total amount of the components (A) to (J) is preferably 0.1 to 20% by mass. From the viewpoint of obtaining sufficient sensitivity, the ratio is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and still more preferably 0.5% by mass or more. On the other hand, from the viewpoint of obtaining a high resolution and suppressing aggregation in the developer, the ratio is preferably 20% by mass or less, and more preferably 10% by mass or less.

(D) Iron atom

In the present embodiment, the content of iron atoms in the photosensitive resin composition layer is 0.01ppm to 10ppm, based on the photosensitive resin composition layer.

The lower limit of the content of iron atoms in the photosensitive resin composition layer is 0.01ppm or more based on the photosensitive resin composition layer.

When the content of the iron atom is less than the above range, the interaction with the metal surface of the substrate becomes weak, and adhesion failure is likely to occur. For example, since iron ions that can exist stably have a valence of 3, CuO can be present on the surface of the substrate^-Forming a coordinate bond with a carboxylic acid of the binder (e.g., CuO)^-…Fe³⁺…COO^-). When the content of the iron atom is not less than the lower limit, the interaction with the metal surface of the substrate is enhanced, and the adhesiveness is excellent.

The content of iron atoms in the photosensitive resin composition layer may be 0.03ppm or more, and may be 0.05ppm or more. Further, the content may be 0.1ppm or more, may be 0.2ppm or more, may be 0.3ppm or more, may be 0.4ppm or more, may be 0.5ppm or more, may be 0.6ppm or more, may be 0.7ppm or more, may be 0.8ppm or more, may be 0.9ppm or more, and may be 1.0ppm or more. Further, it may be 1.1ppm or more, 1.2ppm or more, 1.3ppm or more, 1.4ppm or more, and 1.5ppm or more. The content of the surfactant may be 2.0ppm or more, 3.0ppm or more, 4.0ppm or more, and 5.0ppm or more. The higher the content of iron atoms, the higher the adhesion.

On the other hand, the upper limit of the content of iron atoms in the photosensitive resin composition layer is 10ppm or less based on the photosensitive resin composition layer.

When the content of the iron atom exceeds the above range, the iron ion generates a coordinate bonding bond between molecules, thereby generating pseudo crosslinking. Due to this pseudo-crosslinking, the solubility in the developer is lowered, and a delay in development time occurs. When the content of iron atoms is not more than the above upper limit, the solubility in the developer is suitable, and the developing time is also suitable.

The content of iron atoms in the photosensitive resin composition layer may be 5.0ppm or less, may be 4.0ppm or less, may be 3.0ppm or less, and may be 2.0ppm or less. Further, it may be 1.5ppm or less, may be 1.4ppm or less, may be 1.3ppm or less, may be 1.2ppm or less, may be 1.1ppm or less, and may be 1.0ppm or less. Further, it may be 0.9ppm or less, may be 0.8ppm or less, may be 0.7ppm or less, may be 0.6ppm or less, may be 0.5ppm or less, may be 0.4ppm or less, may be 0.3ppm or less, may be 0.2ppm or less, may be 0.1ppm or less. The smaller the content of iron atoms, the shorter the development time can be.

The content of iron atoms in the photosensitive resin composition layer is in the range of 0.01ppm to 10ppm, most preferably 0.05ppm to 2.0ppm, based on the photosensitive resin composition layer.

By setting the content of iron atoms to the above range, it is possible to achieve both solubility in a developer, that is, developability, and adhesion to a substrate, particularly a copper substrate. When the developability is good, the resist pattern is not likely to leave residues, and when the adhesiveness to the substrate is good, a finer resist pattern can be formed.

The means for adjusting the content of iron atoms in the photosensitive resin composition layer to be in the range of 0.01ppm to 10ppm is not particularly limited, and for example, various adjustments may be made to each component in the composition of the photosensitive resin composition.

The content of the iron atom in the photosensitive resin composition layer can be determined by the method described in examples.

(E) Calcium atom

In the present embodiment, the content of calcium atoms in the photosensitive resin composition layer is 0.005ppm or more and 5ppm or less based on the photosensitive resin composition layer.

The lower limit of the content of calcium atoms in the photosensitive resin composition layer is 0.005ppm or more based on the photosensitive resin composition layer.

When the content of calcium atoms is less than the above range, the interaction with the metal surface of the substrate becomes weak, and adhesion failure occurs. For example, since calcium ion which can exist stably has a valence of 2, CuO can be present on the surface of the substrate^-Forming a coordinate bond with a carboxylic acid of the binder (e.g., CuO)^-…Ca²⁺…COO^-). When the content of calcium atoms is not less than the lower limit, the interaction with the metal surface of the substrate is enhanced, and the adhesion is excellent.

The content of calcium atoms in the photosensitive resin composition layer may be 0.01ppm or more, 0.03ppm or more, 0.05ppm or more, and 0.08ppm or more. Further, the content may be 0.1ppm or more, may be 0.2ppm or more, may be 0.3ppm or more, may be 0.4ppm or more, may be 0.5ppm or more, may be 0.6ppm or more, may be 0.7ppm or more, may be 0.8ppm or more, may be 0.9ppm or more, and may be 1.0ppm or more. Further, it may be 1.1ppm or more, 1.2ppm or more, 1.3ppm or more, 1.4ppm or more, and 1.5ppm or more. The content of the metal oxide is not less than 2.0ppm, not less than 3.0ppm, and not less than 4.0 ppm. The higher the content of calcium atoms, the higher the adhesion.

On the other hand, the upper limit of the content of calcium atoms in the photosensitive resin composition layer is 5ppm or less based on the photosensitive resin composition layer.

When the content of the calcium atom exceeds the above range, the calcium ion generates a coordinate-bondable bond between molecules, thereby causing pseudo-crosslinking. Due to this pseudo-crosslinking, the solubility in the developer is lowered, and a delay in development time occurs. When the content of calcium atoms is not more than the above upper limit, the solubility in the developer is suitable, and the developing time is also suitable.

The content of calcium atoms in the photosensitive resin composition layer may be 4.0ppm or less, may be 3.0ppm or less, and may be 2.0ppm or less. Further, it may be 1.5ppm or less, may be 1.4ppm or less, may be 1.3ppm or less, may be 1.2ppm or less, may be 1.1ppm or less, and may be 1.0ppm or less. Further, it may be 0.9ppm or less, may be 0.8ppm or less, may be 0.7ppm or less, may be 0.6ppm or less, may be 0.5ppm or less, may be 0.4ppm or less, may be 0.3ppm or less, may be 0.2ppm or less, may be 0.1ppm or less, and may be 0.05ppm or less. The smaller the content of calcium atoms, the shorter the development time can be.

The content of calcium atoms in the photosensitive resin composition layer is in the range of 0.005ppm to 5ppm, and most preferably 0.03ppm to 1.0ppm, based on the photosensitive resin composition layer.

By setting the content of calcium atoms to the above range, it is possible to achieve both solubility in a developer, that is, developability, and adhesion to a substrate, particularly a copper substrate. When the developability is good, the resist pattern is not likely to leave residues, and when the adhesiveness to the substrate is good, a finer resist pattern can be formed.

The means for adjusting the content of calcium atoms in the photosensitive resin composition layer to be in the range of 0.005ppm to 5ppm is not particularly limited, and for example, various adjustments may be made to each component in the composition of the photosensitive resin composition.

The content of calcium atoms in the photosensitive resin composition layer can be determined by the method described in examples.

(F) Aluminum atom

In the present embodiment, the content of aluminum atoms in the photosensitive resin composition layer is 0.005ppm or more and 5ppm or less based on the photosensitive resin composition layer.

The lower limit of the content of aluminum atoms in the photosensitive resin composition layer is 0.005ppm or more based on the photosensitive resin composition layer.

When the content of aluminum atoms is less than the above range, the surface of the metal with the substrateThe interaction between the surfaces becomes weak, and adhesion failure occurs. For example, since aluminum ions that can exist stably have a valence of 3, CuO can be present on the surface of the substrate^-Forming a coordinate bond with a carboxylic acid of the binder (e.g., CuO)^-…Al³⁺…COO^-). When the content of aluminum atoms is not less than the lower limit, the interaction with the metal surface of the substrate is enhanced, and the adhesion is excellent.

The content of aluminum atoms in the photosensitive resin composition layer may be 0.01ppm or more, 0.03ppm or more, 0.05ppm or more, and 0.08ppm or more. Further, the content may be 0.1ppm or more, may be 0.2ppm or more, may be 0.3ppm or more, may be 0.4ppm or more, may be 0.5ppm or more, may be 0.6ppm or more, may be 0.7ppm or more, may be 0.8ppm or more, may be 0.9ppm or more, and may be 1.0ppm or more. Further, it may be 1.1ppm or more, 1.2ppm or more, 1.3ppm or more, 1.4ppm or more, and 1.5ppm or more. The content of the metal oxide is not less than 2.0ppm, not less than 3.0ppm, and not less than 4.0 ppm. The greater the content of aluminum atoms, the higher the adhesion.

On the other hand, the upper limit of the content of aluminum atoms in the photosensitive resin composition layer is 5ppm or less based on the photosensitive resin composition layer.

When the content of the aluminum atom exceeds the above range, the aluminum ion generates a coordinate-bondable bond between molecules, thereby generating pseudo-crosslinking. Due to this pseudo-crosslinking, the solubility in the developer is lowered, and a delay in development time occurs. When the content of aluminum atoms is not more than the above upper limit, the solubility in the developer is suitable, and the developing time is also suitable.

The content of aluminum atoms in the photosensitive resin composition layer may be 4.0ppm or less, may be 3.0ppm or less, and may be 2.0ppm or less. Further, it may be 1.5ppm or less, may be 1.4ppm or less, may be 1.3ppm or less, may be 1.2ppm or less, may be 1.1ppm or less, and may be 1.0ppm or less. Further, it may be 0.9ppm or less, may be 0.8ppm or less, may be 0.7ppm or less, may be 0.6ppm or less, may be 0.5ppm or less, may be 0.4ppm or less, may be 0.3ppm or less, may be 0.2ppm or less, may be 0.1ppm or less, and may be 0.05ppm or less.

The content of aluminum atoms in the photosensitive resin composition layer is in the range of 0.005ppm to 5ppm, preferably 0.02ppm to 2.5ppm, and most preferably 0.03ppm to 1.0ppm, based on the photosensitive resin composition layer.

When the content of aluminum atoms is in the above range, the solubility in a developer, that is, the developability and the adhesion to a substrate, particularly a copper substrate can be both satisfied. When the developability is good, the resist pattern is not likely to leave residues, and when the adhesiveness to the substrate is good, a finer resist pattern can be formed.

The means for adjusting the content of aluminum atoms in the photosensitive resin composition layer to be in the range of 0.005ppm to 5ppm is not particularly limited, and for example, various adjustments may be made to each component in the composition of the photosensitive resin composition.

The content of aluminum atoms in the photosensitive resin composition layer can be determined by the method described in examples.

The content of iron atoms, calcium atoms, and aluminum atoms in the photosensitive resin composition layer is preferably 0.02ppm to 20 ppm.

The content of iron atoms, calcium atoms and aluminum atoms may be 0.03ppm or more, 0.04ppm or more, 0.05ppm or more, 0.06ppm or more, 0.07ppm or more, 0.08ppm or more, 0.09ppm or more, and 0.1ppm or more. Further, the content of the metal oxide may be 0.1ppm or more, may be 0.11ppm or more, may be 0.12ppm or more, may be 0.13ppm or more, may be 0.14ppm or more, may be 0.15ppm or more, may be 0.16ppm or more, may be 0.17ppm or more, may be 0.18ppm or more, may be 0.19ppm or more, and may be 0.2ppm or more. Further, the content of the metal oxide may be 0.3ppm or more, 0.4ppm or more, 0.5ppm or more, 0.6ppm or more, 0.7ppm or more, 0.8ppm or more, 0.9ppm or more, and 1.0ppm or more. Further, it may be 1.5ppm or more, 2.0ppm or more, 2.5ppm or more, 3.0ppm or more, 3.5ppm or more, and 4.0ppm or more.

The content of iron atoms, calcium atoms and aluminum atoms may be 15ppm or less, may be 10ppm or less, may be 5ppm or less, may be 4ppm or less, may be 3ppm or less, may be 2ppm or less, and may be 1ppm or less. Preferably 0.11ppm to 5 ppm.

(I) Sodium atom

In the present embodiment, the content of sodium atoms in the photosensitive resin composition layer is 1ppm or more and 50ppm or less based on the photosensitive resin composition layer.

The lower limit of the content of sodium atoms in the photosensitive resin composition layer is 1ppm or more based on the photosensitive resin composition layer.

When the content of sodium atoms is less than the above range, residues are likely to be generated between the formed wirings. By including a small amount of sodium ions in the photosensitive resin composition, the permeability of the developer and the washing water is excellent, and therefore, development can be performed without generating residue even between dense wirings.

The content of sodium atoms in the photosensitive resin composition layer may be 1ppm or more, may be 1.5ppm or more, may be 2ppm or more, may be 3ppm or more, may be 4ppm or more, may be 5ppm or more, may be 6ppm or more, may be 7ppm or more, may be 8ppm or more, may be 9ppm or more, and may be 10ppm or more. The content of the surfactant may be 15ppm or more, 16ppm or more, 17ppm or more, 18ppm or more, 19ppm or more, and 20ppm or more. Further, it may be 30ppm or more, 35ppm or more, 40ppm or more, and 45ppm or more. The more the content of sodium atoms is, the less likely residue is generated between wirings.

On the other hand, the upper limit of the content of sodium atoms in the photosensitive resin composition layer is 50ppm or less based on the photosensitive resin composition layer.

When the content of sodium atoms exceeds the above range, the permeability of the developer and the washing water is too high, and thus the formed dense wiring pattern swells and comes into contact with adjacent wiring, and the dense wiring pattern cannot be obtained. When the content of sodium atoms is not more than the above upper limit, the permeability of the developer and the washing water is appropriate, and the resolution of the dense pattern is excellent.

The content of sodium atoms in the photosensitive resin composition layer may be 45ppm or less, may be 40ppm or less, may be 35ppm or less, and may be 30ppm or less. The content of the metal oxide is 25ppm or less, 20ppm or less, 19ppm or less, 18ppm or less, 17ppm or less, 16ppm or less, and 15ppm or less. Further, it may be 9ppm or less, 8ppm or less, 7ppm or less, 6ppm or less, 5ppm or less, 4ppm or less, 3ppm or less, and 2ppm or less.

The content of sodium atoms in the photosensitive resin composition layer is in the range of 1ppm to 50ppm, preferably 1.5ppm to 25ppm, and most preferably 2ppm to 10ppm, based on the photosensitive resin composition layer.

By setting the content of sodium atoms to the above range, contact between the residue between the wirings and the pattern is prevented, and thus the dense wiring pattern is excellent in formability.

The means for adjusting the content of sodium atoms in the photosensitive resin composition layer to be in the range of 1ppm to 50ppm is not particularly limited, and examples thereof include: the composition of the photosensitive resin composition is variously adjusted for each component, removed by using an ion exchange resin, or added with various sodium salt compounds.

The content of sodium atoms in the photosensitive resin composition layer can be determined by the method described in examples.

(G) Sensitizers

In the photosensitive resin composition of the present embodiment, the (G) sensitizer contains at least 1 selected from a pyrazoline compound, an anthracene compound, a triarylamine compound, and an oxazole compound. These compounds have a large absorption of light around 405nm called h-ray. By using these compounds as a sensitizer, sensitivity and image formability are improved. Among them, the (G) sensitizer more preferably contains at least 1 selected from a pyrazoline compound and an anthracene compound.

The (G) sensitizer is preferably 0.005 to 2% by mass based on the total mass of the solid components of the photosensitive resin composition. By using the sensitizer (G) in this range, good sensitivity, resolution, and adhesion can be obtained.

The sensitizer (G) in the present invention may be one whose sensitivity is improved by combining it with the initiator (C). As the function of the (G) sensitizer, there are enumerated: various functions such as absorption of light of an exposure wavelength, supply of energy or electrons to the initiator, acceleration of cleavage of the initiator (C), generation of an initiating radical or a growing radical by the initiator (C) upon temporary addition to a monomer, transfer of a growing radical after polymerization to the sensitizer (G), and regeneration of a radical by new cleavage and decomposition.

Examples of the (G) sensitizer other than the pyrazoline compound, the anthracene compound, the triarylamine compound, and the oxazole compound include an N-aryl- α -amino acid compound, an alkylamino-substituted aromatic ketone compound, a dialkylaminobenzoate compound, a pyrazoline derivative, an anthracene derivative, a triphenylamine derivative, an ester compound of an N-arylamino acid, and a halogen compound.

Examples of the N-aryl- α -amino acid compound include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine. Particularly, N-phenylglycine is preferable because of its high sensitizing effect.

Examples of the alkylamino-substituted aromatic ketone compound include michler's ketone [4, 4' -bis (dimethylamino) benzophenone ], 4 '-bis (diethylamino) benzophenone, and 4-methoxy-4' -dimethylamino benzophenone.

Examples of the dialkylaminobenzoate compounds include ethyl dimethylaminobenzoate, ethyl diethylaminobenzoate, ethyl p-dimethylaminobenzoate, and 2-ethylhexyl 4- (dimethylamino) benzoate.

As the pyrazoline derivative, from the viewpoint of adhesiveness and rectangularity of resist pattern, 5- (4-tert-butylphenyl) -3- (4-tert-butylstyryl) -1-phenyl-2-pyrazoline, 5- (4-tert-butylphenyl) -1-phenyl-3- (4-phenylphenyl) -4, 5-dihydro-1H-pyrazole, 1-phenyl-3- (4-isopropylstyryl) -5- (4-isopropylphenyl) -pyrazoline, 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl) -pyrazoline, 1-phenyl-3- (4-methoxystyryl) -5- (4- Methoxyphenyl) -pyrazoline, 1-phenyl-3- (3, 5-dimethoxystyryl) -5- (3, 5-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (3, 4-dimethoxystyryl) -5- (3, 4-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2, 6-dimethoxystyryl) -5- (2, 6-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2, 5-dimethoxystyryl) -5- (2, 5-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2, 3-dimethoxystyryl) -5- (2, 3-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2, 4-dimethoxystyryl) -5- (2, 4-dimethoxyphenyl) -pyrazoline, 1-phenyl-3, 5-bis (4-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3, 5-bis (4-methoxy-phenyl) -pyrazoline, 1-phenyl-3- (4-methoxy-phenyl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-tert-butyl-phenyl) -5- (4-methoxy-phenyl) -pyrazoline, and pharmaceutically acceptable salts thereof, 1-phenyl-3- (4-isopropyl-phenyl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-tert-butyl-phenyl) -5- (4-isopropyl-phenyl) -pyrazoline, 1-phenyl-3- (4-methoxy-phenyl) -5- (4-isopropyl-phenyl) -pyrazoline, 1-phenyl-3- (4-isopropyl-phenyl) -5- (4-methoxy-phenyl) -pyrazoline, 1, 5-diphenyl-3- (4-tert-butyl-phenyl) -pyrazoline, 1, 3-diphenyl-5- (4-tert-butyl-phenyl) -pyrazoline, 1, 5-diphenyl-3- (4-isopropyl-phenyl) -pyrazoline, 1, 3-diphenyl-5- (4-isopropyl-phenyl) -pyrazoline, 1, 5-diphenyl-3- (4-methoxy-phenyl) -pyrazoline, 1, 3-diphenyl-5- (4-methoxy-phenyl) -pyrazoline, 1-phenyl-3, 5-bis (4-tert-butyl-phenyl) -pyrazoline, 1, 5-diphenyl-3- (4-tert-butyl-phenyl) -pyrazoline.

Preference is given to 1-phenyl-3- (4-biphenyl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-tert-octyl-phenyl) -pyrazoline.

As the anthracene compound, preferred are anthracene, 9, 10-dialkoxyanthracene, 9, 10-dimethoxyanthracene, 9, 10-diethoxyanthracene, and 9, 10-dibutoxyanthracene. Among them, 9, 10-dibutoxyanthracene is more preferable from the viewpoint of sensitivity. Examples of the triarylamine compound include compounds having a triphenylamine skeleton in the molecule.

The triarylamine compound is preferably a compound represented by the following formula (2).

In the above general formula (2), R₁、R₂And R₃Each independently represents a linear or branched alkyl group having 1 to 10 carbon atoms or a linear or branched alkoxy group having 1 to 4 carbon atoms. n4, n5 and n6 represent integers of 0 to 5 selected so that the value of n4+ n5+ n6 is 1 or more. When n4 is 2 or more, a plurality of R's are present₁The same or different, and when n5 is 2 or more, a plurality of R's are present₂The same or different, and when n6 is 2 or more, a plurality of R's are present₃May be the same or different.

From the viewpoint of resolution and adhesion, the compound represented by the general formula (2) is preferably R₂Is a linear or branched alkyl group having 1 to 10 carbon atoms, n4 and n6 are 0, and n5 is 1. More preferably R₂Is a linear or branched alkyl group having 1 to 4 carbon atoms, n4 and n6 are 0, and n5 is 1.

As the oxazole compound, a compound having an oxazole skeleton in a molecule is exemplified. From the viewpoint of sensitivity, 5-tert-butyl-2- [5- (5-tert-butyl-1, 3-benzoxazol-2-yl) thiophen-2-yl ] -1, 3-benzoxazole, 2- [4- (1, 3-benzoxazol-2-yl) naphthalen-1-yl ] -1, 3-benzoxazole are preferable.

Examples of the ester compound of an N-arylamino acid include methyl ester of N-phenylglycine, ethyl ester of N-phenylglycine, N-propyl ester of N-phenylglycine, isopropyl ester of N-phenylglycine, 1-butyl ester of N-phenylglycine, 2-butyl ester of N-phenylglycine, t-butyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, hexyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, and octyl ester of N-phenylglycine.

Examples of the halogen compound include amyl bromide, isoamyl bromide, bromoisobutylene, vinyl bromide, diphenylmethyl bromide, benzyl bromide, dibromomethane, tribromomethylphenylsulfone, carbon tetrabromide, tris (2, 3-dibromopropyl phosphate), trichloroacetamide, amyl iodide, isobutyl iodide, 1,1, 1-trichloro-2, 2-bis (p-chlorophenyl) ethane, a triazine chloride compound, and a diallyl iodonium compound, and tribromomethylphenylsulfone is particularly preferable.

(H) Additive agent

In the present disclosure, the term "(H) additive" refers to a component blended to impart a desired function to the photosensitive resin composition, and includes components other than the above-described components (a), (B), (C), (D), (E), (F), (G), (I), and (J).

From the viewpoint of preventing the substrate from being reddened, the additive (H) contains a carboxybenzotriazole. The carboxyl benzotriazoles are contained in an amount of 0.01 to 5 mass% based on the total amount of the components (A) to (J). From the viewpoint of preventing the substrate from being reddened when the photosensitive resin laminate is laminated on a substrate such as a copper-clad laminate and development is performed after a lapse of time, the blending amount thereof needs to be 0.01 mass% or more, preferably 0.03 mass% or more, and more preferably 0.05 mass% or more. On the other hand, from the viewpoint of obtaining a high resolution, the blending amount thereof needs to be 5% by mass or less, preferably 3% by mass or less, and more preferably 1% by mass or less.

Examples of the carboxybenzotriazole include 4-carboxy-1, 2, 3-benzotriazole, 5-carboxy-1, 2, 3-benzotriazole, 1- [ N, N-bis (2-ethylhexyl) aminomethyl ] -5-carboxybenzotriazole containing an aminomethyl group which may be substituted, 1- [ N, N-bis (2-ethylhexyl) aminomethyl ] -4-carboxybenzotriazole, 1- [ N, N-bis (isopropyl) aminomethyl ] -5-carboxybenzotriazole, 1- [ N-hydro-N-3- (2-ethylhexyloxy) -1-propylaminomethyl ] -5-carboxybenzotriazole, 1- [ N, N-bis (1-octyl) aminomethyl ] -5-carboxybenzotriazole, 1-carboxy-benzotriazole, 1-hydroxy-N-3- (2-ethylhexyloxy) -1-propylaminomethyl ] -5-carboxybenzotriazole, and mixtures thereof, 1- [ N, N-bis (2-hydroxypropyl) aminomethyl ] -5-carboxybenzotriazole, 1- [ N, N-bis (1-butyl) aminomethyl ] -5-carboxybenzotriazole and the like. Of these, 1- [ N, N-bis (1-butyl) aminomethyl ] -5-carboxybenzotriazole is preferable from the viewpoint of the property of preventing reddening. The substitution position of the carboxyl group may be a mixture of the 5-position and the 6-position during the synthesis, but both are preferable. For example, 0.5: 1.5-1.5: 0.5 (mass ratio), in particular 1: 1 (mass ratio). Also sometimes referred to simply as "1-N-dibutylaminomethylcarboxybenzotriazole" indicates a mixture of a substituent at the 5-position and a substituent at the 6-position. As the carboxybenzotriazole, for example, a compound described in Japanese patent laid-open No. 2008-175957 can be used. Further, 2-mercaptobenzimidazole, 1H-tetrazole, 1-methyl-5-mercapto-1H-tetrazole, 2-amino-5-mercapto-1, 3, 4-thiadiazole, 3-amino-5-mercapto-1, 2, 4-triazole, 3-mercaptotriazole, 4, 5-diphenyl-1, 3-oxadiazol-2-yl, 5-amino-1H-tetrazole, and the like can be used.

Examples of other additives that can be added as component (H) to the photosensitive resin composition include colorants, radical polymerization inhibitors, benzotriazoles other than carboxybenzotriazoles, epoxy compounds of bisphenol a, and plasticizers.

Examples of the coloring agent include fuchsin, phthalocyanine GREEN, auramine base (auramine base), parafuchsin, crystal violet, methyl orange, nile BLUE 2B, victoria BLUE, malachite GREEN (for example, AIZEN (registered trademark) MALACHITEGREEN, manufactured by bakkaiba CHEMICAL corporation), alkali BLUE 20, adamantine GREEN (for example, AIZEN (registered trademark) DIAMOND GREEN, manufactured by bakkaiba CHEMICAL corporation), 1, 4-bis (4-methylphenylamino) -9, 10-anthraquinones (for example, organic CHEMICAL synthesis co, ltd. manufactured, opas GREEN533), 1, 4-bis (butylamino) anthraquinones (for example, organic CHEMICAL synthesis co, ltd. manufactured, OIL BLUE 2N), 1, 4-bis (isopropylamino) -9, 10-anthraquinones (for example, organic CHEMICAL synthesis, ltd. manufactured, BLUE 630), and the like.

The ratio of the colorant to the total amount of the components (A) to (J) is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, even more preferably 0.5 to 2% by mass, and particularly preferably 0.5 to 1% by mass.

As the colorant, for example, a leuco dye or a fluoran dye may be contained. When the photosensitive resin composition layer contains these components, the exposed portion of the photosensitive resin composition layer develops color, and therefore, the photosensitive resin composition layer is preferable from the viewpoint of visibility, and when a position alignment mark for exposure is read by an inspection machine or the like, the exposed portion and the unexposed portion have a large contrast and are easily recognized.

Examples of the leuco dye include tris (4-dimethylaminophenyl) methane [ leuco crystal violet ], bis (4-dimethylaminophenyl) phenylmethane [ leuco malachite green ], and the like. In particular, leuco crystal violet is preferably used as the leuco dye from the viewpoint of improving contrast. The content of the leuco dye in the photosensitive resin composition is preferably 0.1 to 10% by mass relative to the total amount of the components (A) to (J). From the viewpoint of improving the contrast between the exposed portion and the unexposed portion, the content is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and particularly preferably 0.4% by mass or more. On the other hand, from the viewpoint of maintaining storage stability, the content is preferably 10% by mass or less, more preferably 2% by mass or less, and particularly preferably 1% by mass or less.

In addition, from the viewpoint of optimizing the adhesion and the contrast, it is preferable to use a leuco dye and a halogen compound in combination in the photosensitive resin composition. The halogen compound may be derived from the above-mentioned organic halogen compound as the component (C), and tribromomethylphenylsulfone is particularly preferable.

Examples of the radical polymerization inhibitor include p-methoxyphenol, hydroquinone, biphenyltriol, naphthylamine, t-butylcatechol, cuprous chloride, 2, 6-di-t-butyl-p-cresol, 2 '-methylenebis (4-methyl-6-t-butylphenol), 2' -methylenebis (4-ethyl-6-t-butylphenol), nitrosophenylhydroxylamine aluminum salt, and diphenylnitrosamine. The nitrosophenylhydroxylamine aluminum salt is preferable in order not to impair the sensitivity of the photosensitive resin composition.

Examples of benzotriazoles other than carboxybenzotriazoles include 1,2, 3-benzotriazole, 1-chloro-1, 2, 3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1, 2, 3-tolyltriazole, and bis (N-2-hydroxyethyl) aminomethylene-1, 2, 3-benzotriazole.

Examples of the epoxy compound of bisphenol a include compounds obtained by modifying bisphenol a with polypropylene glycol and epoxidizing the terminal.

The total content of the radical polymerization inhibitor, the benzotriazole other than carboxybenzotriazole, carboxybenzotriazole and the epoxy compound of bisphenol A is preferably 0.001 to 3% by mass, more preferably 0.01 to 1% by mass, based on the total amount of the components (A) to (J). From the viewpoint of imparting storage stability to the photosensitive resin composition, the content is preferably 0.001% by mass or more, and from the viewpoint of maintaining the sensitivity of the photosensitive resin composition and suppressing discoloration and color development of the dye, the content is preferably 3% by mass or less.

Examples of the plasticizer include phthalic acid esters such as diethyl phthalate, o-toluenesulfonamide, p-toluenesulfonamide, tributyl citrate, triethyl citrate, acetyl tri-n-propyl citrate, acetyl tri-n-butyl citrate, polyethylene glycol, polypropylene glycol, polyethylene glycol alkyl ether, and polypropylene glycol alkyl ether. In addition, there may be enumerated: ADEKANOL SDX-1569, ADEKANOL SDX-1570, ADEKANOL SDX-1571, and ADEKANOL SDX-479 (available from Asahi Denka Co., Ltd.); newpol BP-23P, Newpol BP-3P, Newpol BP-5P, Newpol BPE-20T, Newpol BPE-60, Newpol BPE-100, Newpol BPE-180 (manufactured by Sanyo Kaisha Co., Ltd.); UniolDB-400, Uniol DAB-800, Uniol DA-350F, Uniol DA-400, Uniol DA-700 (manufactured by Nippon fat and oil Co., Ltd.); and compounds having a bisphenol skeleton such as BA-P4U Glycol and BA-P8 Glycol (manufactured by Nippon emulsifier Co., Ltd.).

The content of the plasticizer is preferably 1 to 50% by mass, more preferably 1 to 30% by mass, based on the total amount of the components (A) to (J). From the viewpoint of suppressing the delay of the development time and imparting flexibility to the cured film, the content is preferably 1% by mass or more, and from the viewpoint of suppressing insufficient curing and cold flow, the content is preferably 50% by mass or less.

< photosensitive resin laminate >

The photosensitive resin laminate of the present embodiment includes a support film, and a photosensitive resin composition layer containing a photosensitive resin composition provided on the support film.

Another embodiment provides a photosensitive resin laminate in which a photosensitive resin composition layer containing the photosensitive resin composition described above is laminated on a support film. The photosensitive resin laminate may have a protective layer on the surface of the photosensitive resin composition layer on the opposite side to the supporting film side, as necessary.

The support film is preferably a transparent support film that transmits light emitted from the exposure light source. Examples of such a support film include a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, a vinylidene chloride copolymer film, a polymethyl methacrylate copolymer film, a polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, and a cellulose derivative film. These films may be stretched as necessary, and preferably have a haze of 5 or less. The thinner the film thickness is, the better the image formability and the economical efficiency are, so that it is advantageous to use a film of 10 to 30 μm in order to maintain the strength of the photosensitive resin laminate.

Important characteristics of the protective layer used for the photosensitive resin laminate are: the adhesion force between the protective layer and the photosensitive resin composition layer is sufficiently smaller than the adhesion force between the support film and the photosensitive resin composition layer, and the protective layer can be easily peeled off. For example, a polyethylene film or a polypropylene film may be preferably used as the protective layer. Further, a film having excellent releasability, as shown in, for example, Japanese patent application laid-open No. 59-202457, can be used. The thickness of the protective layer is preferably 10 to 100 μm, and more preferably 10 to 50 μm.

When polyethylene is used as the protective layer, gels called fish eyes exist on the surface of the polyethylene film, and these gels may be transferred to the photosensitive resin composition layer. When the fish eye is transferred to the photosensitive resin composition layer, air may be involved in lamination to form a void, which may cause a defect of the resist pattern. The material of the protective layer is preferably stretched polypropylene from the viewpoint of preventing fish eyes. Specific examples thereof include ALPHAN E-200A manufactured by Wangzi paper (Ltd.).

The thickness of the photosensitive resin composition layer in the photosensitive resin laminate varies depending on the application, and is preferably 5 to 100 μm, more preferably 7 to 60 μm, and the resolution is improved as the thickness is smaller, and the film strength is improved as the thickness is thicker.

< method for producing photosensitive resin laminate >

A method for producing a photosensitive resin laminate will be described.

The method for producing a photosensitive resin laminate of the present embodiment includes: a preparation liquid production step of producing the photosensitive resin composition preparation liquid; and a coating and drying step of coating the photosensitive resin composition preparation liquid on a support film and drying the coating to form a photosensitive resin composition layer, thereby producing the photosensitive resin laminate.

As a method for producing a photosensitive resin laminate by sequentially laminating a support film, a photosensitive resin composition layer, and a protective layer to be used as needed, a known method can be employed. For example, a photosensitive resin composition used for the photosensitive resin composition layer is mixed with a solvent in which the composition can be dissolved to prepare a uniform solution (photosensitive resin composition preparation solution).

Suitable solvents include: ketones such as acetone, Methyl Ethyl Ketone (MEK), etc.; and alcohols such as methanol, ethanol, isopropanol, and the like. The solvent is preferably added to the photosensitive resin composition so that the viscosity of the photosensitive resin composition preparation liquid at 25 ℃ is from 500 mPa.s to 4000 mPa.s.

Then, the photosensitive resin composition preparation liquid is first coated on a support film by a bar coater or a roll coater, and then dried, thereby laminating a photosensitive resin composition layer containing a photosensitive resin composition on the support film. Next, a protective layer is laminated on the photosensitive resin composition layer as necessary, whereby a photosensitive resin laminate can be produced.

< method for forming resist pattern >

Another embodiment provides a resist pattern forming method including: and laminating the photosensitive resin laminate on a substrate, and exposing and developing the laminate. An example of a method for forming a resist pattern using the photosensitive resin laminate of the present embodiment will be described below. Examples of the resist pattern include resist patterns formed on a circuit board (printed wiring board), a flexible substrate, a lead frame substrate, a substrate for COF (chip on film), a substrate for a semiconductor package, a transparent electrode for a liquid crystal panel, a TFT wiring for a liquid crystal panel, a wiring for an organic EL display, an electrode for PDP (plasma display panel), and the like.

The resist pattern can be formed through the following steps.

The resist pattern forming method of the present embodiment includes: laminating the photosensitive resin laminate on a substrate; exposing the photosensitive resin composition layer; and a step of developing the exposed photosensitive resin composition layer.

(1) Lamination process

The photosensitive resin laminate is bonded to a substrate such as a copper-clad laminate or a flexible substrate by a hot roll laminator while the protective layer of the photosensitive resin composition layer is peeled off. The lamination conditions may be set as appropriate among the conventionally known conditions.

(2) Exposure Process

A mask film having a desired pattern (e.g., a wiring pattern) is brought into close contact with a support film of the photosensitive resin laminate and exposed to light using an active light source, or a drawing pattern corresponding to the desired pattern is exposed by direct drawing. The exposure is preferably performed by direct writing of a writing pattern. As the exposure wavelength, i-ray, h-ray, g-ray, a mixed ray thereof, and the like can be suitably used. The photosensitive resin composition of the present embodiment is advantageous in that high sensitivity and high resolution can be achieved in exposure to i-rays or h-rays, particularly h-rays. In addition, this makes the photosensitive resin composition of the present embodiment useful particularly for direct drawing. The exposure conditions may be set as appropriate among conventionally known conditions.

(3) Developing process

After exposure, the support film on the photosensitive resin composition layer is peeled off, and then an unexposed portion is developed and removed with a developer of an aqueous alkali solution, thereby forming a resist pattern on the substrate. As the aqueous alkali solution, Na was used₂CO₃Aqueous solutions or K₂CO₃An aqueous solution. The aqueous alkali solution is suitably selected depending on the characteristics of the photosensitive resin composition layer, and is usually Na having a concentration of about 0.2 to 2% by mass and a temperature of about 20 to 40 ℃₂CO₃An aqueous solution.

Though the resist pattern can be obtained through the above steps, a heating step of about 100 to 300 ℃ may be further performed according to circumstances. By performing this heating step, chemical resistance can be further improved. As the heating, a heating furnace of a hot air, infrared ray or far infrared ray system may be used.

The method for forming a metal wiring of the present embodiment includes: a step of forming a resist pattern by the above method; a step of forming a metal wiring (conductor pattern) using the resist pattern; and a step of stripping the resist pattern.

Another embodiment provides a method for manufacturing a circuit board including steps of laminating the photosensitive resin laminate on a base material and performing exposure, development, and plating, and a method for manufacturing a circuit board including steps of laminating the photosensitive resin laminate on a base material and performing exposure, development, and etching. The circuit substrate can be manufactured by further etching or plating the base material on which the resist pattern is formed in the steps described above with respect to the resist pattern forming method. In particular, when exposure is performed by direct drawing of a drawing pattern in the manufacture of a circuit board, it is not necessary to form a mask, and therefore, this is advantageous from the viewpoint of productivity. Etching and plating may be performed as follows, respectively.

(4) Etching or plating process

The surface of the substrate exposed by the development (for example, the copper surface in the case of a copper-clad laminate) is etched or plated to form a conductor pattern. As for the etching and plating methods, conventionally known methods can be suitably used, respectively.

(5) Peeling step

Then, the resist pattern is peeled off from the substrate with an aqueous solution having a stronger alkalinity than the developer. The alkaline aqueous solution for stripping is not particularly limited, and usually an aqueous NaOH solution or an aqueous KOH solution having a concentration of about 2 to 5% by mass and a temperature of about 40 to 70 ℃ is used. A small amount of a water-soluble solvent may be added to the stripping solution.

In particular, in the present embodiment, by using a diphenylpyrazoline derivative as the (G) photosensitizer, the stripping property after plating is particularly excellent.

Through the steps described above, a circuit substrate can be manufactured.

In addition, the method for manufacturing a semiconductor package according to the present embodiment provides a method for manufacturing a semiconductor package, including: forming a resist pattern on a substrate for a semiconductor package as a base material by the above resist pattern forming method; and a step of etching or plating the substrate for a semiconductor package on which the resist pattern is formed. The substrate for a semiconductor package and the structure of the semiconductor package can be any conventionally known substrate and structure. In addition, the formation of the resist pattern, and the etching or plating may be performed separately according to the above steps.

The photosensitive resin laminate of the present embodiment is a photosensitive resin laminate suitable for manufacturing conductor patterns of circuit boards (printed wiring boards), flexible boards, lead frame boards, substrates for COF (chip on film), substrates for semiconductor packages, transparent electrodes for liquid crystal panels, TFT wiring for liquid crystal panels, wiring for organic EL displays, electrodes for PDPs (plasma display panels), and the like.

As described above, according to the present embodiment, it is possible to provide a photosensitive resin laminate and a method for manufacturing the same, which can achieve both solubility in a developer, that is, developability, and adhesion to a substrate, particularly a copper substrate.

Unless otherwise specified, the various parameters described above are measured by the measurement methods in the examples described below.