TWI789796B - Polymer and application thereof - Google Patents

Abstract

The present invention provides a polymer comprising a structure of formula (I): wherein the definitions of each variable are provided herein. By means of the polymer, the resin composition of the present invention is able to forming a film with low haze and low coefficient of thermal expansion.

Description

Polymers and their applications

The present invention relates to a polymer having at least one of a phenolic hydroxyl group and an amide group (-CONH ₂ ) in the side chain, and particularly relates to a polymer that can be used to form an adhesive film with low haze and low expansion coefficient.

In the manufacture of semiconductor devices, insulating materials, such as die adhesive films, build-up films, and underfills, are required from the cutting of semiconductor element dies to the bonding of each other, or the connection between semiconductor elements and semiconductor wafers. For circuit design and packaging. With the demand for miniaturization and high performance of electronic components, the designed IC chips also require miniaturization and high integration. For this reason, in 2.5D or 3D flip-chip packaging, the electrode pitch (electrode pitch) on the semiconductor element, the distance between chips and the semiconductor element connected by bumps are shortened, and the adhesive film and filler used also need to increase toughness, Insulation to cope with the evolution of IC packaging. As a packaging method using die adhesive film, build-up film and underfill, at present, after the electrode is placed on the semiconductor element, the semiconductor element uses the die adhesive film to assist in cutting and transferring the wafer, and the build-up film is used for 3D stacking to increase the performance and conduction of the semiconductor element. The upper and lower layers of circuits and underfill are used to protect semiconductor devices, etc. for semiconductor element packaging.

However, depending on the packaging method, the miniaturization of the electrode pitch, or the shortening of the inter-wafer distance between semiconductor elements, insulating materials such as die-bonding films, build-up films, and underfills, Cracking during dicing and build-up and filling of voids tend to be difficult, and bonding reliability may decrease.

Therefore, in order to increase the cracking resistance and pore filling of the material, flexible resins, such as thermoplastic resins such as polyamide and polyimide (patent document TW 202033655A), or flexible thermosetting hardening resins, Such as aliphatic epoxy resin, liquid acrylic polymer (patent document TW202041594A)), or flexible hardener, such as aliphatic mercaptan (patent document TW 201936689A) or the comprehensive use of flexible materials above. Adding flexible resin can reduce cracking and warping problems, but there are still many issues to be solved in terms of balancing material storage, film handling, resin compatibility and CCD alignment problems and large thermal expansion coefficients.

In view of the above technical problems, the object of the present invention is to provide a resin composition, the resin film formed by it has low haze and low thermal expansion coefficient.

其中，X各自獨立為四價有機基團；Y各自獨立為二羧酸之二價殘基；E各自獨立為-NH-或-O-； A及B係各自獨立為二價有機基團，且A及B中至少一者為下述式(II)所示之基團或式(III)所示之基團：

其中，q為0~3中之任一整數；Q各自獨立為單鍵、-CH₂-、-C₂H₂-、-C₂H₄-、-C₃H₆-、-C₄H₈-、-C(CH₃)₂-、-C(CF₃)₂、-O-、-CO-、-CONH-、-COO-、-S(O)₂-、-S(O)₂NH-、-CH₂CO-、-CH₂CONH-或亞茀基(fluorenylidene)；及R¹各自獨立為-OH、-CONH₂或-L-Ph-R²，其中L各自獨立為單鍵、-CH₂-、-C₂H₂-、-C₂H₄-、-C₃H₆-、-C₄H₈-、-C(CH₃)₂-、-C(CF₃)₂、-O-、-CO-、-CONH-、-COO-、-S(O)₂-、-S(O)₂NH-、-CH₂CO-或-CH₂CONH-；R²各自獨立為-OH或-CONH₂；m及n各自獨立為0~300中之任一整數，但m與n不同時為0；及該聚合物包含至少一個該式(II)所示之基團或式(III)所示之基團，且該聚合物係符合下述條件(i)及條件(ii)中之至少一者： (i)羥價為50~500(KOH)mg/g；(ii)胺價為50~500(HClO₄)mg/g。 To achieve the above object, the present invention provides a kind of polymer, its weight average molecular weight is 1,000～100,000, and it comprises the structure shown in formula (I):

Wherein, X is each independently a tetravalent organic group; Y is each independently a divalent residue of a dicarboxylic acid; E is each independently -NH- or -O-; A and B are each independently a divalent organic group, And at least one of A and B is a group shown in the following formula (II) or a group shown in formula (III):

Wherein, q is any integer from 0 to 3; each Q is independently a single bond, -CH ₂ -, -C ₂ H ₂ -, -C ₂ H ₄ -, -C ₃ H ₆ -, -C ₄ H ₈ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ , -O-, -CO-, -CONH-, -COO-, -S(O) ₂ -, -S(O) ₂ NH-, -CH ₂ CO-, -CH ₂ CONH- or fluorenylidene; and R ¹ are each independently -OH, -CONH ₂ or -L-Ph-R ² , wherein L is each independently a single bond , -CH ₂ -, -C ₂ H ₂ -, -C ₂ H ₄ -, -C ₃ H ₆ -, -C ₄ H ₈ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ , -O-, -CO-, -CONH-, -COO-, -S(O) ₂ -, -S(O) ₂ NH-, -CH ₂ CO- or -CH ₂ CONH-; each R ² is independently is -OH or -CONH ₂ ; m and n are each independently any integer from 0 to 300, but m and n are not 0 at the same time; and the polymer contains at least one group represented by the formula (II) or A group represented by formula (III), and the polymer meets at least one of the following conditions (i) and (ii): (i) the hydroxyl value is 50~500 (KOH) mg/g; ( ii) The amine value is 50~500 (HClO ₄ ) mg/g.

，其中Q、R¹、R²及L之定義如上所述。 Preferably, the group represented by the formula (II) is selected from:

, wherein Q, R ¹ , R ² and L are as defined above.

、

或

，其中R¹及R²之定義如上述。 More preferably, the group shown in the formula (II) is selected from:

,

or

, wherein R ¹ and R ² are as defined above.

Preferably, the molar percentage of the group represented by the formula (II) or formula (III) is 10-100% of the total repeating unit.

The present invention also provides a resin composition, which comprises: the aforementioned polymer; an epoxy resin; a hardener; and an inorganic filler.

Preferably, the resin composition further includes at least one of a hardening accelerator and a silane coupling agent.

Preferably, the haze of the film formed from the resin composition is 50 or less.

Preferably, the cured film formed by the resin composition has a storage elastic modulus of 1.8 or more at 50°C.

The present invention further provides a resin film formed from the aforementioned resin composition.

The present invention further provides an adhesive film, which includes: a base material; and the aforementioned resin film, which is configured on the base material.

Preferably, the resin film has a haze of 50 or less.

The present invention further provides a printed circuit board, which includes an insulating layer, and the insulating layer is a hardened product of the aforementioned resin film.

The present invention further provides a semiconductor device, which includes the aforementioned printed circuit board.

The present invention can form a low haze and Resin composition of prepreg with good compatibility.

In the present invention, "*" indicates a linking point.

In the present invention, "divalent residue of dicarboxylic acid" refers to the residue after removing two carboxyl groups (-COOH) from a dicarboxylic acid compound or removing two -C(O)Cl groups from a diacyl chloride compound The divalent group. An example is given below:

In the present invention, "quaternary residue of tetracarboxylic dianhydride" refers to the residue of tetracarboxylic dianhydride compound after removing two dicarboxylic anhydride groups (-C(O)-O-C(O)-). Quadrivalent group.

In the present invention, the "divalent residue of diamine" refers to the divalent group remaining after the two amine groups are removed from the diamine compound.

In the present invention, the "divalent residue of a diol" refers to the divalent group remaining after removing two amine groups from a diol compound.

The resin composition provided by the present invention comprises: a polymer; an epoxy resin; a curing agent; and an inorganic filler.

In the present invention, the polymer comprises the structure shown in formula (I):

In formula (I), each occurrence of X may be the same or different, and may be a tetravalent organic group. Preferably, the tetravalent organic group is a tetravalent residue of tetracarboxylic dianhydride. Examples of the tetracarboxylic dianhydride include, but are not limited to: bisphenol A diether dianhydride, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride, pyromellitic dianhydride (PMDA) , 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-bis Phenylphenyl tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2 ,2',3,3'-Diphenylmethanetetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-Diphenylmethane Ketone tetracarboxylic dianhydride, 4,4'-oxodiphthalic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,7-naphthalene tetracarboxylic dicarboxylic acid anhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4- Dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride , 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 1,8,9,10-phenanthrene tetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride and their alkyl derivatives with 1 to 6 carbons and/or Alkoxy derivatives with 1 to 6 carbon atoms.

In formula (I), each occurrence of Y may be the same or different, and may be a divalent residue of a dicarboxylic acid. Examples of dicarboxylic acid compounds suitable for use in the present invention include, but are not limited to: aliphatic dicarboxylic acids having 3 to 20 carbon atoms, aromatic dicarboxylic acids having 8 to 20 carbon atoms. Examples of the aliphatic dicarboxylic acid include, but are not limited to: malonic acid, dimethylmalonic acid, maleic acid, dimethylmaleic acid, succinic acid, glutaric acid, 2,2-dimethylpentane Diacid, adipic acid, 2,3-diethylsuccinic acid, 2-methyladipic acid, trimethyladipic acid, Pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1, 3-Cyclopentane dicarboxylic acid, norbornane dicarboxylic acid, tricyclodecane dicarboxylic acid, pentacyclododecane dicarboxylic acid, citric acid, citraconic acid, itaconic acid. Examples of the aromatic dicarboxylic acid include, but are not limited to: phthalic acid, terephthalic acid, isophthalic acid, 2-methylterephthalic acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene Dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, benzophenone-4,4'-dicarboxylic acid, diphenylphenone -4,4'-dicarboxylic acid, 4,4'-biphenyl dicarboxylic acid. These dicarboxylic acid compounds can be used individually or in combination of 2 or more types (for example: 3 types, 4 types, 5 types). Examples of diacyl chloride compounds may be sebacyl chloride, 4,4'-oxybis(benzoyl chloride), or the corresponding diacyl chloride compounds of the above-mentioned dicarboxylic acid compounds. For example: the corresponding diacyl chloride compound of malonic acid is malonyl chloride; the corresponding diacyl chloride compound of adipic acid is adipyl chloride. In the present invention, the dicarboxylic acid compound can be used in combination with the diacyl chloride compound.

In formula (I), each occurrence of E may be the same or different, and may be -NH- or -O-.

In formula (I), A and B are each independently a divalent organic group (which may be a divalent residue of a diamine or a divalent residue of a diol), and at least one of A and B is the following The group shown in formula (II) or the group shown in formula (III):

In formula (II), q is any integer from 0 to 3, that is, q can be 0, 1, 2 or 3.

In formula (II), each occurrence of Q may be the same or different, and may be a single bond, -CH ₂ -, -C ₂ H ₂ -, -C ₂ H ₄ -, -C ₃ H ₆ -, - C ₄ H ₈ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ , -O-, -CO-, -CONH-, -COO-, -S(O) ₂ -, -S( O) ₂ NH-, -CH ₂ CO-, -CH ₂ CONH- or fluorenylidene.

In formula (II), each occurrence of R ¹ may be the same or different, and may be OH, -CONH ₂ or -L-Ph-R ² , wherein L is each independently a single bond, -CH ₂ -, -C ₂ H ₂ -, -C ₂ H ₄ -, -C ₃ H ₆ -, -C ₄ H ₈ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ , -O-, -CO- , -CONH-, -COO-, -S(O) ₂ -, -S(O) ₂ NH-, -CH ₂ CO- or -CH ₂ CONH-. Wherein, each occurrence of R ² may be the same or different, and may be -OH or -CONH ₂ . For example, since L can be a single bond, R ¹ can be each independently -Ph-R ² .

，其中Q、R¹、R²及L之定義同上。 In a preferred embodiment, the group represented by the formula (II) is selected from:

, wherein Q, R ¹ , R ² and L are as defined above.

或

，其中R¹之定義如上所述。 In certain embodiments, Q in formula (II) is a single bond. Examples where Q is a single bond may be:

or

, wherein R ¹ is as defined above.

，其中R²定義如上所述。 In some embodiments, in formula (II), q is 0; R ¹ is -L-Ph-R ² , wherein L is a single bond. Examples of this formula (II) may be:

, wherein R ² is as defined above.

，其中R¹之定義如上所述。 In some embodiments, Q is fluorenylidene, that is, the group represented by the formula (II) can be:

, wherein R ¹ is as defined above.

In formula (III), the definition of R ¹ is the same as in formula (II).

In the present invention, examples of the diamine compound include but are not limited to: 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane, 2,2'-bis(trifluoromethyl)- 4,4'-diaminobiphenyl, 3,5-diaminophenol, 4,4'-diaminodiphenyl ether, 4,4'-methylene bis-(2-aminobenzamide), 1 ,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6 -Diaminohexane, 1,2-diaminocyclopentane, 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane , 1,4-diaminocyclohexane, 1,2-bis-(aminomethyl)cyclohexane, 1,3-bis-(aminomethyl)cyclohexane, 1,4-bis- (Aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethyl Cyclohexylmethane, isophorone diamine, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, polyphenylene ether diamine, diaminotoluene, 4,4'-diaminobiphenyl, 3 ,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,3 '-Diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 3 ,3'-diaminodiphenyl sulfide, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4 '-Diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2 ,2-bis-(4-aminophenyl)propane, 2,2-bis-(4-aminophenyl)hexafluoropropane, 2,2-bis-(3-hydroxy-4-aminophenyl) ) propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis-(3-amino-4-hydroxyphenyl)propane, 2,2-bis- (3-amino-4-hydroxyphenyl)hexafluoropropane, bis-(3-amino-4-hydroxyphenyl)pyridine, bis-(4-amino-3-hydroxyphenyl)pyridine, 4, 4'-diamino-terphenyl, 4,4'-bis-(4-aminophenoxy)biphenyl, bis-[4-(4-aminophenoxy)phenyl]pyridine, bis[ 4-(3-aminophenoxy)phenyl]pyridine, bis[4-(2-aminophenoxy)phenyl]pyridine, 1,3-bis-(4-aminophenoxy)benzene , 1,4-bis-(4-aminophenoxy)benzene, 9,10-bis-(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diamine 1,3-bis-(4-aminophenoxy)benzene, 1,3-bis-(3-aminophenoxy)benzene, 1,3-bis-(4-amine phenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'- Diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl] Hexafluoropropane, 9,9-bis-(4-aminophenyl)-10-hydroanthracene, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy -4,4'-diaminobiphenyl, 9,9'-bis-(4-aminophenyl) terpene, 4,4'-dimethyl-3,3'-diaminodiphenyl , 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4-diaminocumene, 2,5-diaminocumene, 2,5-Dimethyl-p-phenylenediamine, Acetylguanamine, 2,3,5,6-Tetramethyl-p-phenylenediamine, 2,4,6-Trimethyl-m-phenylenediamine, Bis(3-aminopropyl)tetramethyldisiloxane, 2,5-diaminopyridine, 1,2-bis-(4-aminophenyl)ethane, diaminobenzylaniline , diaminobenzoate, 1,5-diaminonaphthalene, diaminotrifluorotoluene, 1,3-bis-(4-aminophenyl) hexafluoropropane, 1,4-bis-( 4-aminophenyl)octafluorobutane, 1,5-bis-(4-aminophenyl)decafluoropentane, 1,7-bis-(4-aminophenyl)tetrafluoroheptane , 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2 ,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3 ,5-bis-(trifluoromethyl)phenyl]hexafluoropropane, 4,4'-bis-(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis -(4-Amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis-(4-amino-2-trifluoromethylphenoxy)diphenylene, 4, 4'-bis-(3-amino-5-trifluoromethylphenoxy)diphenylphenoxide, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy) Phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis-(tri Fluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorobenzidine, 4,4'-diaminoquaterphenylenediamine, 3,3',5,5 '-Tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis-(trifluoromethyl)biphenyl, 2,2',5,5 ',6,6'-Hexafluorobenzidine.

In the specific example for the purpose of flexibility, the diol compound is preferably a diol having at least two alkylene groups in the main chain, and the diamine compound is preferably a diol having at least two alkylene groups in the main chain. Diamines of alcohol chains and/or propylene glycol chains. Examples of the diamine compound include, but are not limited to: JEFFAMINE (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D- 2000, D-4000 (the above is the product name, manufactured by HUNTSMAN), 1-(2-(2-(2-aminopropane Oxy)ethoxy)propoxy)propane-2-amine, 1-(1-(1-(2-aminopropoxy)propane-2-ethoxy)propoxy)propane-2- amine. Examples of the diol compound also include: dihydroxydiphenylmethane (such as: 4,4'-dihydroxydiphenylmethane), dihydroxybenzamide (such as: 3,5-dihydroxybenzamide), But not limited to this.

In some embodiments, the molar percentage of the group derived from the diamine compound represented by the formula (II) or formula (III) is 10-100% of the total repeating units. In a preferred embodiment, the group represented by the formula (II) or formula (III) derived from diamine accounts for 15-70% of the total number of moles of repeating units. In a better embodiment, the group derived from the formula (II) or formula (III) of the diamine compound is 20-50% (such as: 22-48% , 25~45%, 25~47%).

In formula (I), m and n are each independently any integer of 0 to 300 (such as: 0, 20, 40, 60, 80, 100, 120, 140, 160, 180, 200, 220, 240, 260, 280, 300), but m and n are not 0 at the same time, such as: m is 0, n is 1; m is 1, n is 0.

In the present invention, the polymer contains at least one group represented by the formula (II) or the group represented by the formula (III), and the polymer meets the following conditions (i) and conditions (ii) At least one of them: (i) the hydroxyl value is 50~500 (KOH) mg/g (such as: 60~450, 75~450, 75~400 mg/g); (ii) the amine value is 50~500 (HClO ₄ )mg/g (such as: 60~450, 75~450, 75~400mg/g).

In the present invention, the weight average molecular weight (Mw) is 1,000~100,000, preferably 5,000~70,000, more preferably 10,000~50,000 (such as: 11,000~49,000, 12,000~48,000, 13,000~47,000). When the Mw is too low, the strength of the molded article is likely to be impaired, while if the Mw is too high, the handleability and processability may be deteriorated. In the present invention, Mw is measured by gel permeation chromatography (GPC). When the non-volatile component in the resin composition is 100% by mass, the content of the polymer is preferably 0.01% by mass to 50% by mass.

In certain embodiments, the polymers of the present invention are polyimides. The polyimide can be prepared by the following method. Firstly, a diamine compound is reacted with tetracarboxylic dianhydride to obtain a polyimide precursor (such as polyamic acid), and then a cyclodehydration reaction is performed to convert it into polyimide. The specific implementation method of the imidization process can be chemical imidization or thermal imidization. Add dehydrating agent and/or imidization catalyst to polyimide precursor (such as: polyamide acid polyamide ester or polyamide-amide solution), at 0℃~100℃ The chemical reaction is carried out at high temperature to complete imidization. Alternatively, the polyimide compound after dehydration, dealcoholization or deamination can be obtained by heating the solution to reflux. When producing the polyimide precursor or polyimide, the process of precipitating solid may be included. Specifically, polyamide in a solvent (such as: tetrahydrofuran, dimethylacetamide, N, N-diethylacetamide, diethylformamide, N-methylpyrrolidone) is made The imine precursor or polyimide is precipitated in a solvent (water, alcohols), or other methods capable of solid precipitation. Then, the obtained solid is dried to obtain a powdery polyimide precursor or polyimide.

The end-capping agent suitable for the present invention is preferably monoamine, monoacid anhydride, monocarboxylic acid, monoacyl chloride compound or monoactive ester compound. The end-capping agent is more preferably a monoacid anhydride or a monoamine. Examples of such monoanhydrides include, but are not limited to: trimellitic anhydride, (methyl)phthalic anhydride, (methyl)hydrophthalic anhydride, dodecenylsuccinic anhydride, methyl (hydrogenated) nadic anhydride, formic Butenyl tetrahydrophthalic anhydride, etc. Examples of the monoamine include, but are not limited to: aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene , 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene , 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene , 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, Amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminobenzene Thiophenol, 3-aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-(2-aminoethylamino)propyldimethoxymethylsilane, 3-(2- Aminoethylamino)propyltriethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane. These end-blocking agents can be used alone or in combination of two or more (such as three or four). In the present invention, a plurality of different terminal groups can also be introduced into the polymer structure by using a plurality of end-capping agents. The end-capping agent can make the polymer have better storage stability.

Examples of organic solvents used in the preparation of polyimide precursors include, but are not limited to: γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, acetone, methyl ethyl ketone, butanone, Cyclohexanone, cyclopentanone, hydroxyhexanone, hydroxypentanone, toluene, xylene, trimethylbenzene, tetramethylbenzene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether , ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol ether, triethylene glycol monoethyl ether, acetic acid Ethyl ester, butyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol butyl ether acetate, dimethyl dicarboxylate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate , dipropylene glycol monomethyl ether acetate, dimethyl dicarboxylate, methanol, ethanol, propanol, ethylene glycol, propylene glycol, carbitol, dimethylacetamide, N,N-diethylacetamide Amine, dimethylformamide, N-methylpyrrolidone, N-ethylpyrrolidone, 1,3-dimethyl-2-imidazolinone, N,N-dimethylmethoxyacetamide, di Methylsulfide, N-methylcaprolactam, tetrahydrofuran, dichloromethane, dichloroethane, chloroform, 1,2-dimethoxyethane, bis(2-methoxyethyl) ether. These organic solvents can be used individually or in combination of 2 or more types (for example: 3 types, 4 types).

In the heating cyclodehydration reaction, imidization catalysts can be used, such as: methylamine, ethylamine, trimethylamine, triethylamine, propylamine, tripropylamine, butylamine, tributylamine, tert-butylamine, pentylamine, hexylamine , triethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, triethylenediamine, 1-methylpyrrole Alkane, 1-ethylpyrrolidine, aniline, benzylamine, toluidine, trichloroaniline, imidazole, methylimidazole, dimethylimidazole, pyridine, picoline, lutidine, collidine, triazole , Methyltriazole, quinoline, methylquinoline, isoquinoline, methylisoquinoline, valerolactone. These catalysts can be used individually or in combination of 2 or more types (for example: 3 types, 4 types). In addition, in the heating cyclodehydration reaction, an azeotropic dehydrating agent may be used, examples of which include: toluene, xylene, ethylcyclohexane, but not limited thereto. These azeotropic dehydrating agents can be used alone or in combination of two or more (such as three or four).

In the chemical imidization method, pyridine, picoline, triethylamine, diisopropylethylamine, or quinoline may be used as an imidization catalyst (such as a dehydration ring-closing catalyst), but is not limited thereto. Other examples of catalysts include saturated or unsaturated nitrogen-containing heterocyclic compounds, amino acid compounds, aromatic hydrocarbon compounds or aromatic heterocyclic compounds with hydroxyl groups. For example: 1,2-dimethylimidazole, 1-methylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 5-methylbenzimidazole, N-benzyl-2-methyl imidazole, diazole derivatives, triazole derivatives, quinoline, isoquinoline, 2,4-lutidine, 2,5-lutidine, 3,4-lutidine, 3,5 - Lutidine. These catalysts can be used individually or in combination of 2 or more types (for example: 3 types, 4 types). In addition, acetic anhydride, propionic anhydride, butyric anhydride, or benzoic anhydride can be used as the dehydrating agent for dehydration and ring closure. These dehydrating agents may be used alone or in combination of two or more (such as three or four).

In some embodiments, the polymer is polyamide. The polyamide can be prepared by the following method. At a reaction temperature of -50 to 200°C, the diamine compound is reacted with the dicarboxylic acid compound or diacyl chloride compound to obtain polyamide. The diamine compound can be selected from m-phenylenediamine (mPD), p-phenylenediamine (PPD), p-phenylenediamine , m-xylylenediamine, 1,3,6-benzenetriamine (TAB), 4-chloro-1,3-phenylenediamine, 6-chloro-1,3-phenylenediamine, 3-chloro-1, 4-phenylenediamine, tetramethylenediamine, pentamethylenediamine, 2-methylpentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nine Methylenediamine, Decamethylenediamine, Nonanediamine, Methylpentamethylenediamine, Dodecanediamine, 2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 1,3-diaminocyclohexane, 1,4- Diaminocyclohexane, methylcyclohexanediamine, isophordiamine, norbornanedimethylamine, tricyclodecanedimethyldiamine, 1,3-bis-(aminomethyl)cyclohexane alkane, 1,4-bis-(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, 2,2-bis-(4-aminocyclohexyl)propane, 4,4'-diamino Diphenylmethane, 4,4'-diaminodiphenylene, 4,4'-diaminodiphenyl ether bis-(aminomethyl)decalin, bis-(aminomethyl)tricyclodecane, bis- (4-aminophenyl)ether, p-phenylenediamine or bis-(aminomethyl)naphthalene. These diamine compounds can be used individually or in combination of 2 or more types (for example: 3 types, 4 types).

Examples of organic solvents used in the preparation of polyamides include, but are not limited to: γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, acetone, methyl ethyl ketone, butanone, cyclohexane Ketone, cyclopentanone, hydroxyhexanone, hydroxypentanone, toluene, xylene, trimethylbenzene, tetramethylbenzene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethyl Glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol ether, triethylene glycol monoethyl ether, ethyl acetate , butyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol butyl ether acetate, dimethyl dicarboxylate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, two Propylene glycol monomethyl ether acetate, dimethyl dicarboxylate, methanol, ethanol, propanol, ethylene glycol, propylene glycol, carbitol, dimethylacetamide, N,N-diethylacetamide, Dimethylformamide, diethylformamide, N-methylpyrrolidone, N-ethylpyrrolidone, 1,3-dimethyl-2-imidazolinone, N,N-dimethylmethoxy Acetamide, dimethylsulfoxide, N-methylcaprolactam, tetrahydrofuran, dichloromethane, dichloroethane, chloroform, 1,2-dimethoxyethane, bis(2-methyl Oxyethyl) ether. These organic solvents can be used individually or in combination of 2 or more types (for example: 3 types, 4 types).

The structure represented by the formula (I) contains a polyester structure, therefore, the polymer of the present invention can be a polyester. The polyester structure is obtained by reacting a diol compound (such as diphenol) with a dicarboxylic acid compound or a diacyl chloride compound at a reaction temperature of 50-300°C. The diol compound can be ethylene glycol, diethylene glycol, propylene glycol, 2-methyl-1,3-propanediol in addition to the compound that forms the group shown in formula (II) or formula (III) , 2,2-diethyl-1,3-propanediol, trimethylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, diethylene glycol, Triethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol, cyclopentanediol, cyclohexanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,2-decalin dimethanol, 1,3-decalin dimethanol, 1,4-decalin dimethanol, 1,5-decalin dimethanol, 1,6-decalin dimethanol, 2,7-decalin dimethanol, tetrahydronaphthalene dimethanol, norbornane dimethanol, tricyclodecane dimethanol, pentacyclododecane dimethanol, 4,4 '-(1-methylethylene) bisphenol, methylene bisphenol (alias: bisphenol F), 4,4'-cyclohexylidene bisphenol (alias: bisphenol Z), 4,4' -Sulphonyl bisphenol (alias: bisphenol S), resorcinol, hydroquinone, 4,4-dihydroxybiphenyl, 4,4'-dihydroxybenzophenone, 2,2-bis (4-hydroxyphenyl)propane, 4,4' -dihydroxydiphenyl ether, 4,4' -dihydroxydiphenylbenzophenone, 1,1-bis(4-hydroxyphenyl)-3, 3,5-trimethylcyclohexane, 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, bis(4- hydroxyphenyl)diphenylmethane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(3-phenyl-4-hydroxyphenyl)propane, 2,2 -Bis(4-hydroxy-3-tert-butylphenyl)propane, 1,3-bis(2-(4-hydroxyphenyl)propyl)benzene, 1,4-bis(2-(4-hydroxyphenyl) Base) propyl) benzene 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane (hereinafter also referred to as "spirodiol"), 5-hydroxymethyl-5-ethyl-2-(1,1-dimethyl-2-hydroxyethyl)-1,3-dioxane (hereinafter also referred to as "Dioxanediol"), 9,9-bis(4-diyl-3-methylphenyl)fluorene, the above-mentioned derivatives. These diol compounds may be used alone or in combination of two or more (such as three or four).

In the present invention, examples of the epoxy resin include but are not limited to: bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol A & F type epoxy resin, Dicyclopentadiene type epoxy resin, triphenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, Tert-butylcatechol-type epoxy resin, naphthalene-type epoxy resin, naphthol-type epoxy resin, anthracene-type epoxy resin, glycidylamine-type epoxy resin, glycidyl ester-type epoxy resin, cresol novolac Varnish-type epoxy resins, biphenyl-type epoxy resins, linear aliphatic epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, spiro-ring-containing epoxy resins, cyclohexanedimethanol-type epoxy resins , naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, butylene oxide compound. These epoxy resins can be used individually or in combination of 2 or more types (for example, 3 types, 4 types). Examples of commercially available epoxy resins include, but are not limited to: EPICLON HM-101, 830, 840, 850, 860, N-660, N-690, N-695, N-730A, N-739, N- 740, N-770, HP4032, HP4032D, HP4032H, HP-4700, HP-4710, HP5000, HP7200, HP7200H, HP7200L, EXA-4700, EXA-4770, EXA-4816, EXA-4822, EXA-4850-150, EXA-4850-1000, EXA-859CRP (DIC), 4004P, jER807, jER828, jER152, YL6121, YL7760, YL7800, YX4000, YX4000H, YX4000HK, YX8800 (Mitsubishi Chemical), PETG (Showa Denko), ZX1059 (New Nippon Steel Chemical), NC3000, NC3000H, NC3000L, NC6000, NC7000, NC7000L, EXA7311, (Nippon Kayaku), TEPIC-S, TEPIC-VL (Nissan Chemical), EP-4088L (ADEKA), ELM-100, ELM-434 ( Sumitomo Chemical), EX-721 (Nagase), Selokiside 2021P, PB-3600, PB-3600M (Daicel), EP-4003S, EP-4000S (ADEKA), YD-134, YDC-1312, YSLV-90C, YSLV -120TE (Kukodo Chemical), ESN-475V, ESN-485 (Toto Chemical), BEO-60E (New Nippon Chemical), OXT-121, OXT-221, OXT-191, OXT-223 (East Asia Synthetic), GE23 , GE24, GE35, GE36, DA323, RK4850 (CVC), analogs thereof. These commercially available epoxy resins may be used alone or in combination of two or more (such as three or four). In general, a resin composition with excellent flexibility can be obtained by using the above-mentioned liquid, crystalline or solid epoxy resins in combination. In addition, the breaking strength of the cured product of the resin composition is also improved.

The epoxy resin system of the present invention may additionally have a polyphenylene oxide structure. The epoxy resin with polyphenylene oxide structure can be obtained through the addition polymerization reaction of diphenol compound and bifunctional epoxy resin at the reaction temperature of -50~200°C. Other specific examples of epoxy resins may be bisphenol A type phenoxy resins (such as YP-50, YP-50S and YP-55U manufactured by Nippon Steel & Sumikin Chemicals, jER1256 by Mitsubishi Chemical, PKHA by Gabriel Phenoxies), bisphenol A Phenol F type phenoxy resins (such as Phenototox FX-316 manufactured by Nippon Steel & Sumikin Chemicals), bisphenol A & F copolymer type phenoxy resins (such as Phenototox YP-70 and ZX1356- 2), Bisphenol S-containing phenoxy resin (Mitsubishi Chemical YX8100) nonylphenol EO modified acrylate (Aronix M-113 manufactured by Toagosei), nonylphenol EO modified acrylate (Aronix manufactured by Toagosei) M-111), phenol EO-modified acrylate (Aronix M-101A, M-102 manufactured by Toagosei), phenoxyethyl acrylate (light acrylate PO-A of Kyoei Chemical), 3-phenyl acrylate Oxybenzyl ester (POB-A of Kyoei Chemical), 2-hydroxy-3-phenoxypropyl acrylate (Epoxy Ester M-600A of Kyoei Chemical), and other types of phenoxy resins (such as Xinri Phenototox (YPB-43C, FX280, FX293, EXA-123 from DIC, jER4275, YX6954BH30, YX7200B35, YX7553, YL7769BH30 from Mitsubishi Chemical) manufactured by Tetsusumikin Chemical Co., Ltd., or the like. These epoxy resins can be used individually or in combination of 2 or more types (for example, 1 type, 4 types).

From the standpoint of expressing the properties of the insulating layer, when the non-volatile components in the resin composition are 100% by mass, the content of the epoxy resin is preferably at least 5% by mass, more preferably at least 10% by mass. If it is necessary to improve the mechanical strength and insulation reliability, the content of the epoxy resin is more than 15% by mass. The upper limit of the content of the epoxy resin is not particularly limited as long as it can exhibit the effect of the present invention.

In the present invention, the curing agent has the function of curing the epoxy resin, and its examples include but are not limited to: phenolic curing agent, naphthol-based curing agent, cyanate-based curing agent, benzoxazine-based curing agent , Carbodiimide series, amine curing agent. These curing agents can be used alone or in combination of two or more (such as: three, Four) use. From the point of view of improving chemical resistance and insulation, the curing agent is preferably PT30, PT60, BA230 (Lonza), HFB2006M (Showa Polymer), V-03, V-07 (Nisshinbo Chemical), MEH-7700, MEH-7810, MEH-7851 (Meiwa Kasei), NHN series, CBN series, GPH series (Nippon Kayaku), SN-170, SN-180, SN-190, SN-475, SN-485, SN-495, SN-375, SN-395 (Nippon Steel & Sumikin Chemical), LA-7052, LA-7054, LA-3018, LA-1356, ATN series, HPC-8000-65T, TD2090 (DIC), 4,4'- Diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethoxybiphenyl, 4, 4'-Diaminophenylbenzoate, 1,5-diaminonaphthalene, 1,3-diaminonaphthalene, 1,4-diaminonaphthalene, 1,8-diaminonaphthalene, or the like. These epoxy resins can be used individually or in combination of 2 or more types (for example, 1 type, 4 types).

When the non-volatile components in the resin composition are 100% by mass, the content of the curing agent in the resin composition is preferably 10% by mass to 70% by mass, more preferably 15% by mass to 40% by mass.

In the present invention, the inorganic filler is mainly used to improve mechanical strength and reduce thermal expansion coefficient. Examples of the inorganic filler include, but are not limited to: silica, crystalline silica, non-fiber glass, glass powder, talc, hydrotalcite, boehmite, cordierite, clay, mineral wool, natural mica, synthetic mica, carbonic acid Magnesium, calcium carbonate, barium sulfate, barium zirconate, calcium zirconate, zirconium phosphate, magnesium titanate, calcium titanate, strontium titanate, barium titanate, bismuth titanate, boron nitride, aluminum nitride, manganese nitride , iron oxide, titanium oxide, zirconium oxide, magnesium oxide, aluminum oxide, aluminum hydroxide, aluminum silicate, calcium silicate, spangles or the like. Among them, the inorganic filler is preferably spherical silica from the viewpoint of small specific gravity, high filling rate of the cured product, and easy improvement of strength. These inorganic fillers can be used individually or in combination of 2 or more types (for example: 3 types, 4 types).

In the present invention, the average particle size of the inorganic filler is not particularly limited. From the viewpoint of reducing surface roughness and filling properties, it is preferably less than 3 μm, and more preferably in consideration of good wiring formability. The average particle diameter is 1 μm or less. The lower limit of the average particle size is not particularly limited, but it is preferably 0.01 μm or more. Examples of commercially available inorganic fillers include, but are not limited to: UFP-30 (Electrochemical Industry), YC100C, YA050C, YA050C-MJE, YA010C, SO-C2, SO-C1 (Admatechs), Silfil NSS-3N, Silfil NSS-4N, Silfil NSS-5N (Tokuyama).

The inorganic filler is preferably a surface-treated inorganic filler to introduce curable reactive groups to the surface of the inorganic filler. Here, the curable reactive group is not particularly limited as long as it is a group cured with an alkali-soluble resin or an epoxy resin, and may be a photocurable reactive group or a thermosetting reactive group. Examples of the photocurable reactive group include but are not limited to: methacrylic group, acrylic group, vinyl group, styrene group. Examples of the thermosetting reactive group include, but are not limited to: epoxy, isocyanate, amino, imino, imino, hydroxyl, carboxyl, mercapto, methoxymethyl, methoxyethyl, ethoxy methyl, ethoxyethyl, oxazolinyl, oxetanyl. The method for introducing curable reactive groups to the surface of the inorganic filler is not particularly limited, and can be introduced by using known and commonly used methods, or can be treated with a surface treatment agent having curable reactive groups. Curable reactive groups are introduced into the surface of the inorganic filler. The surface of the inorganic filler can be treated with an organic or inorganic group coupling agent. Examples of the coupling agent include but are not limited to: silane coupling agents (such as: methacrylic acid, diphenyl diamino), titanium coupling agents, zirconium coupling agents, aluminum coupling agents. Examples of inorganic fillers that are not surface treated with curable reactive groups include, but are not limited to: silica-alumina surface treatment, titanate-based coupling agent treatment, aluminate-based coupling agent treatment, or organic treatment. Inorganic filler.

As the surface-treated coupling agent for the inorganic filler, silane-based, titanate-based, aluminate-based, zircoaluminate-based coupling agents, etc. can be used. Among them, silane coupling agents are preferred, examples of which include but are not limited to: vinyltrimethoxysilane, vinyltriethoxysilane, N-(2-aminomethyl)-3-aminopropylmethyldi Methoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-anilinopropyltrimethoxysilane, 3-cyclo Oxypropoxypropyltrimethoxysilane, 3-Glycidoxypropylmethyldimethoxysilane, 2-((3,4-epoxy)cyclohexyl)ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane silane, 3-mercaptopropyltrimethoxysilane or the like. These coupling agents can be used alone or in combination of two or more (such as three or four). These silane coupling agents are preferably pre-immobilized on the surface of the inorganic filler by adsorption or reaction. Examples of commercially available silane coupling agents include, but are not limited to: YA050C-MJE (Yadomar), MA-ST-L, IPA-ST-L, PMA-ST, EAC-ST, TOL-ST, MEK -ST-40, MEK-ST-L, MEK-EC-2130Y, MEK-AC-2140Z, MEK-AC-4130Y, MEK-AC-5140Z, PGM-AC-2140Y, PGM-AC-4130Y, MIBK-AC -2140Z (Nissan Chemical). These silane coupling agents can be used alone or in combination of two or more (such as three or four).

The average particle size of the surface-treated inorganic filler is preferably less than 5 μm, more preferably 1-0.01 μm. From the viewpoint of obtaining an insulating layer with a low expansion coefficient, when the non-volatile components in the resin composition are 100% by mass, the inorganic filler in the resin composition is preferably at least 40% by mass, more preferably 50% by mass above.

The resin composition of the present invention may or may not further contain additives. Examples of such additives include, but are not limited to: surfactants, colorants, photoinitiators, thermal initiators, polymerization inhibitors, tougheners, plasticizers, elastomers, mercapto compounds, urethanization catalysts , thixotropic agent, adhesion promoter (such as: compounds with imidazolyl, thiazolyl or triazolyl), magnetic particles (such as: magnetic particles of block copolymers), chain transfer agents, copper damage inhibitors, antioxidants , antirust agent, UV absorber, thickener (such as: fine powder silicon dioxide, organic bentonite, etc.), tackifier, defoamer and/or leveling agent (such as: silicone, fluorine, acrylic system, polymer system, etc.), flame retardants (such as: phosphinates, phosphate ester derivatives, phosphorus compounds (such as phosphazene compounds), etc.). These additives may be used alone or in combination of two or more. Wherein the additive is preferably a flame retardant. The flame retardant contained in the resin composition The amount is not particularly limited, but is preferably 0.5% by mass to 20% by mass, more preferably 1% by mass to 15% by mass, and most preferably 1.5% by mass to 10% by mass.

In a preferred embodiment, the resin composition further includes a hardening accelerator and/or a silane coupling agent. Examples of the hardening accelerator include, but are not limited to: 2E4MZ, 2PZ, C17Z, 2MZ-CN, 2MA-OK. Examples of the silane coupling agent include, but are not limited to: KBM-403, KBE-403, X-12-967C (Shin-Etsu), A-187, CoatOSil 2287, CoatOSil MP200 (Momentive). These hardening accelerators and silane coupling agents may be used alone or in combination of two or more (such as three or four).

The resin composition of the present invention can be applied to the production of adhesive films. Specifically, the adhesive film includes a base material and a resin film disposed thereon, wherein the resin film is formed from the aforementioned resin composition. In some embodiments, the method for making the adhesive film includes the following steps: providing a substrate; coating the resin composition of the present invention on the substrate to obtain a coated substrate; The coated substrate is dried so that the resin film formed by the resin composition is dried. If necessary, the dried resin film may be cured to obtain an adhesive film. From the viewpoint of thinning semiconductor devices and printed wiring boards, the thickness of the resin film is preferably at most 100 μm, more preferably at most 80 μm, most preferably at most 60 μm, most preferably at most 50 μm. The lower limit of the thickness of the resin film is not particularly limited, but is preferably greater than 3 μm.

The substrate can be a preformed printed wiring substrate, flexible printed wiring substrate, paper phenolic, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth, all grades (FR-4 etc.) copper foil substrate, fiber cloth epoxy resin, glass cloth/paper epoxy resin, synthetic fiber epoxy resin, fluororesin/polyethylene/polyimide film, polyimide film, PET film, PEN film, PC film, PMMA film, TAC film, glass substrate, ceramic substrate or wafer substrate. If the base material is used as a support material or a protective material, it can be a support material or a protective material with a peeling layer on the surface, wherein the peeling agent in the peeling layer can be: alkyd resin, polyolefin One or more of hydrocarbon resin, polyurethane resin and silicone resin. These release agents are not limited thereto. These base materials can be used individually or in combination of 2 or more types (for example: 3 types, 4 types).

In the present invention, the resin composition can be adjusted to a suitable viscosity for coating with an organic solvent, and then coated. Examples of the coating method include, but are not limited to: dip coating, flow coating, roll coating, rod coater, screen printing, curtain coating. These coating methods may be used alone or in combination of two or more (such as three or four).

In another embodiment, the method for making a dry film protection material with a resin composition comprises the following steps: coating the resin composition of the present invention on a support material to obtain a coated support material; At a temperature of 60~100°C, the surface of the coated support material is dried to volatilize the organic solvent in the resin composition, and then obtain a dry film material with a support material; the support material is obtained by a laminator The dry film material of the material is pressed on the protective material to form a dry film protective material. Afterwards, the dry film material can be pressed onto the substrate by peeling off the protective material.

Volatile drying after coating the resin composition of the present invention can be performed using a hot air circulation drying oven equipped with an air heating type heating device, an IR oven, a hot plate, or a convection oven. The volatile drying can be accomplished by using countercurrent contact with hot air in the machine, and by blowing hot air from nozzles onto the rack.

The resin composition of the present invention is coated on a support material and dried at a temperature of 60-100°C to form a dry film material. After removing the support material, it can be measured by haze, and the lamination haze is below 50%. . The thickness of the dry film material is preferably 50-300 μm.

The side chain of the polymer represented by formula (I) of the present invention has a functional group structure of phenolic hydroxyl group and amide group. In addition to being used as a hardening application in epoxy resin, the present invention finds that different functional groups are set. The 3D network structure formed after hardening can cover the inorganic filler to increase its compatibility and reduce the Low haze and improved chemical resistance, and the hydrogen bond generated by the polar structure can further reduce the thermal expansion coefficient. Therefore, the polymer represented by formula (I) of the present invention can be applied to semiconductor devices, such as printed circuit boards.

The following examples further illustrate the present invention, but they are not intended to limit the scope of the present invention. Any changes and modifications made by those familiar with the technical field of the present invention without departing from the spirit of the present invention are within the scope of the present invention.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. In the following description, unless otherwise specified, "parts" and "%" mean "parts by weight" and "% by weight", respectively.

The meanings represented by the abbreviations used in the examples are organized as follows:

Synthesis Example 1: Hydroxyl-containing polyimide (A-1)

In a 1L separable four-necked flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, add 171g NMP (N-methylpyrrolidone) and 18.31g (50.0mmol) (2,2-bis(3-amino-4 - hydroxyphenyl)-hexafluoropropane). Under stirring and nitrogen protection, all the solids were dissolved to form a homogeneous solution, and the four-necked flask was cooled to 0~5°C with an ice bath. Under stirring, 23.94 g (92.0 mmol) of solid powder of bisphenol A diether dianhydride was added to the above-mentioned homogeneous solution in batches. The resulting mixture was stirred at 150 rpm for 3 hours, then, maleic anhydride (0.39 g, 4.0 mmol) was added as an end-capping agent, and stirred for further 1 hour to obtain a polyamic acid solution. Next, the stirring speed was set to 200 rpm, the polyamic acid solution was heated to 190° C. and kept at the temperature for 2 hours, so as to carry out the dehydration reaction of imidization. After the reaction, the obtained mixture was cooled to room temperature, poured into water to precipitate a precipitate, and the obtained hydroxyl-containing polyimide resin powder was washed with 1:1 methanol/water 1000 g. After the powder was filtered, it was dried in a vacuum oven at 50° C. for 24 hours to obtain 38 g of hydroxyl-containing polyimide resin (A-1) powder.

According to the IR spectrum of A-1, the characteristic (C=O) absorption of the imide ring can be observed at 1769 and 1698 (cm ^-1 ). The intrinsic viscosity of A-1 is 0.30dL/g, the hydroxyl value is 283, and the Mw (GPC) is 12000.

Synthesis Example 2: Hydroxyl-containing polyimide (A-2)

In a 1L separable four-necked flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, add 158g of NMP, 7.33g (20.0mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)-hexa Fluoropropane) and 9.61 g (30.0 mmol) of 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl. Under stirring and nitrogen protection, all the solids were dissolved to form a homogeneous solution, and the four-necked flask was cooled to 0~5°C with an ice bath. Under stirring, 11.97g (23.0mmol) of bisphenol A diether dianhydride and 11.97g (23.0mmol) of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride solid powder were divided into Add in batches to the above homogeneous solution. The resulting mixture was stirred at 150 rpm for 3 hours, then maleic anhydride (0.39 g, 4.0 mmol) was added as an end-capping agent, and stirred for further 1 hour to obtain a polyamic acid solution. Next, the stirring speed was set to 200 rpm, the polyamic acid solution was heated to 190° C. and kept at the temperature for 2 hours, so as to carry out the dehydration reaction of imidization. catch Next, the same purification method as in Synthesis Example 1 was used to obtain 30 g of hydroxyl-containing polyimide resin (A-2) powder. The intrinsic viscosity of A-2 is 0.23dL/g, the hydroxyl value is 180, and the Mw (GPC) is 9000.

Synthesis Example 3: Hydroxyl-Containing Polyimide (A-3)

In a 1L separable four-necked flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, add 153g of NMP, 7.33g (20.0mmol) of APAF, 1.86g (15.0mmol) of 3,5-DAP (3,5 - diaminophenol) and 4.80 g (15.0 mmol) of TFMB. Under stirring and nitrogen protection, all the solids were dissolved to form a homogeneous solution, and the four-necked flask was cooled to 0~5°C with an ice bath. Under stirring, 23.94 g (46.0 mmol) of BPADA solid powder was added in batches to the above homogeneous solution. The resulting mixture was stirred at 150 rpm for 3 hours, then maleic anhydride (0.39 g, 4.0 mmol) was added as an end-capping agent, and stirred for further 1 hour to obtain a polyamic acid solution. Next, the stirring speed was set to 200 rpm, the polyamic acid solution was heated to 190° C. and kept at the temperature for 2 hours, so as to carry out the dehydration reaction of imidization. Next, purification was performed using the same purification method as in Synthesis Example 1 to obtain 29 g of hydroxyl-containing polyimide resin (A-3) powder. The intrinsic viscosity of A-3 is 0.22dL/g, the hydroxyl value is 228, and the Mw (GPC) is 11500.

Synthesis Example 4: Hydroxyl-containing polyimide (A-4)

In a 1L separable four-necked flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, 171g of NMP, 2.48g (20.0mmol) of 3,5-DAP and 23.4g (26.0mmol) of JEFFAMINE ED-900 were added. Under stirring and nitrogen protection, all the solids were dissolved to form a homogeneous solution, and the four-necked flask was cooled to 0~5°C with an ice bath. Under stirring, 13.01 g (25.0 mmol) of BPADA solid powder was added in batches to the above homogeneous solution. The resulting mixture was stirred at 150 rpm for 3 hours, then, KBM-903 (0.72 g, 4.0 mmol) was added as an end-capping agent, and further stirred for 1 hour to obtain a light yellow polyamic acid solution. Next, the stirring speed was set to 200 rpm, the polyamic acid solution was heated to 190° C. and kept at the temperature for 2 hours, so as to carry out the dehydration reaction of imidization. Next, use the same synthesis example 1 The purification method was used for purification to obtain a hydroxyl-containing polyimide resin (A-4). The intrinsic viscosity of A-4 is 0.26dL/g, the hydroxyl value is 121, and the Mw (GPC) is 15600.

Synthesis Example 5: Containing amide group (-CONH ₂ ) of polyester (A-5)

In a 1L separable four-necked flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, add 104g of NMP, 5.01g (25.0mmol) of 4,4'-dihydroxydiphenylmethane and 3.83g (25.0mmol) of 3,5-Dihydroxybenzamide. Under stirring and nitrogen protection, all the solids were dissolved to form a homogeneous solution, and the four-necked flask was cooled to 0~5°C with an ice bath. Under stirring, 5.38 g (22.5 mmol) of sebacyl chloride and 6.64 g (22.5 mmol) of 4,4'-oxybis(benzoyl chloride) solid powder were added to the above homogeneous solution in batches. The resulting mixture was stirred at 150 rpm for 3 hours, during which an appropriate amount of base was added to catalyze the reaction. Next, purification was carried out in the same manner as in Synthesis Example 1 to obtain 11 g of amide group-containing polyester (A-5) powder. The intrinsic viscosity of A-5 is 0.21dL/g, the amine value is 60, and the Mw (GPC) is 13000.

Synthesis Example 6: Amide-containing polyimide (A-6)

In a 1L separable four-necked flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, add 174g of NMP, 4.26g (15.0mmol) of 4,4'-methylenebis-(2-aminobenzamide ) and 12.4 g (31.0 mmol) of JEFFAMINE D-400. Under stirring and nitrogen protection, all the solids were dissolved to form a homogeneous solution, and the four-necked flask was cooled to 0~5°C with an ice bath. Under stirring, 26.02 g (50.0 mmol) of BPADA solid powder was added in batches to the above homogeneous solution. The resulting mixture was stirred at 150 rpm for 3 hours, then, KBM-903 (0.72 g, 4.0 mmol) was added as an end-capping agent, and further stirred for 1 hour to obtain a polyamic acid solution. Next, the stirring speed was set to 200 rpm, the polyamic acid solution was heated to 190° C. and kept at the temperature for 2 hours, so as to carry out the dehydration reaction of imidization. Next, purification was carried out in the same manner as in Synthesis Example 1 to obtain 27 g of amide group-containing polyimide resin (A-6) powder. The intrinsic viscosity of A-6 is 0.35dL/g, the amine value is 160, and the Mw (GPC) is 18000.

Synthesis Example 7: Hydroxyl-Containing Polyamide (A-7)

Add 107g NMP, 9.16g (25.0mmol) of APAF and 5.01g (25.0mmol) of 4,4'-diaminodiphenyl ether into a 1L separable four-necked flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device . Under stirring and nitrogen protection, all the solids were dissolved to form a homogeneous solution, and the four-necked flask was cooled to 0~5°C with an ice bath. Under stirring, 5.38 g (22.5 mmol) of sebacyl chloride and 6.64 g (22.5 mmol) of 4,4'-oxybis(benzoyl chloride) solid powder were added to the above homogeneous solution in batches. The obtained mixture was stirred at 150 rpm for 3 hours, then, maleic anhydride (0.49 g, 5.0 mmol) was added as an end-capping agent, and further stirred for 1 hour. Next, purification was performed using the same purification method as in Synthesis Example 1 to obtain 21 g of hydroxyl-containing polyamide resin (A-7) powder. The intrinsic viscosity of A-7 is 0.31dL/g, the hydroxyl group is 364, and the Mw (GPC) is 17000.

Synthesis Example 8: Hydroxyl-containing polyamide imide (A-8)

156g of NMP, 5.49g (15.0mmol) of APAF and 12.4g (31.0mmol) of JEFFAMINE D-400 were added to a 1L separable four-necked flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device. Under stirring and nitrogen protection, all the solids were dissolved to form a homogeneous solution, and the four-necked flask was cooled to 0~5°C with an ice bath. Under stirring, 7.38 g (25.0 mmol) of 4,4'-oxybis(benzoyl chloride) and 13.01 g (25.0 mmol) of BPADA solid powder were added to the above homogeneous solution in batches. The resulting mixture was stirred at 150 rpm for 3 hours, then, KBM-903 (0.72 g, 4.0 mmol) was added as an end-capping agent, and further stirred for 1 hour to obtain a polyamido-amic acid solution. Then, the stirring speed was set to 200 rpm, and the polyamido-amic acid solution was heated to 180° C. and kept at the temperature for 2 hours, so as to carry out the dehydration reaction of imidization. Next, purification was performed using the same purification method as in Synthesis Example 1 to obtain 22 g of hydroxyl-containing polyamideimide resin (A-8) powder. The intrinsic viscosity of A-8 is 0.29dL/g, the hydroxyl group is 76, and the Mw (GPC) is 15000.

Synthesis Example 9: Hydroxyl-containing polyamide imide (A-9)

In a 1L separable four-neck flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, add 139g of NMP, 5.49g (15.0mmol) of APAF, 6.4g (16.0mmol) of JEFFAMINE D-400 and 1.86g ( 15.0 mmol) of 3,5-DAP. Under stirring and nitrogen protection, all the solids were dissolved to form a homogeneous solution, and the four-necked flask was cooled to 0~5°C with an ice bath. Under stirring, 7.38 g (25.0 mmol) of 4,4'-oxybis(benzoyl chloride) and 13.01 g (25.0 mmol) of BPADA solid powder were added to the above homogeneous solution in batches. The resulting mixture was stirred at 150 rpm for 3 hours, then, KBM-903 (0.72 g, 4.0 mmol) was added as an end-capping agent, and further stirred for 1 hour to obtain a polyamido-amic acid solution. Then, the stirring speed was set to 200 rpm, and the polyamido-amic acid solution was heated to 180° C. and kept at the temperature for 2 hours, so as to carry out the dehydration reaction of imidization. Next, purification was performed using the same purification method as in Synthesis Example 1 to obtain 24 g of hydroxyl-containing polyamideimide resin (A-9) powder. The intrinsic viscosity of A-8 is 0.27dL/g, the hydroxyl group is 110, and the Mw (GPC) is 16600.

Comparative Synthesis Example 1: Polyimide (B-1) without hydroxyl, carboxyl and amide groups

In a 1L separable four-neck flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, 273g of NMP and 41.4g (46.0mmol) of JEFFAMINE ED-900 were added. Under stirring and nitrogen protection, all the solids were dissolved to form a homogeneous solution, and the four-necked flask was cooled to 0~5°C with an ice bath. Under stirring, 26.02 g (50 mmol) of BPADA solid powder was added in batches to the above homogeneous solution. The resulting mixture was stirred at 150 rpm for 3 hours, then, KBM-903 (0.72 g, 4.0 mmol) was added as an end-capping agent, and further stirred for 1 hour to obtain a polyamic acid solution. Then, the stirring speed was set to 200 rpm, and the polyamic acid solution was heated to 190° C. and kept at the temperature for 2 hours to carry out the dehydration reaction of imidization. Next, purification was performed using the same purification method as in Synthesis Example 1 to obtain 47 g of polyimide resin (B-1) powder.

Comparative Synthesis Example 2: Polyamidoimide (B-2) without hydroxyl, carboxyl and amide groups

In a 1L separable four-necked flask equipped with a mechanical stirrer, a thermometer and a nitrogen protection device, 116 g of NMP and 9.21 g (46 mmol) of ODA were added. Under stirring and nitrogen protection, all the solids were dissolved to form a homogeneous solution, and the four-necked flask was cooled to 0~5°C with an ice bath. Under stirring, 5.98 g (25.0 mmol) of sebacyl chloride and 13.01 g (25.0 mmol) of BPADA solid powder were added to the above homogeneous solution in batches. The resulting mixture was stirred at 150 rpm for 3 hours, then, KBM-903 (0.72 g, 4.0 mmol) was added as an end-capping agent, and further stirred for 1 hour to obtain a pale yellow polyamide-amic acid solution. Then, the stirring speed was set to 200 rpm, and the polyamido-amic acid solution was heated to 190° C. and kept at the temperature for 2 hours, so as to carry out the dehydration reaction of imidization. Next, purification was performed using the same purification method as in Synthesis Example 1 to obtain 19 g of polyamide imide resin (B-2) powder.

Embodiment 1～9 and comparative example 1～3

According to the ratio (weight ratio) shown in Table 1, each material was added to methyl ethyl ketone as a solvent, and the mixture was stirred at 1200 rpm for 2 hours with a stirrer to obtain a resin composition. Using an applicator, the obtained resin composition was coated on the release-treated surface of a polyimide film (manufactured by SKC) having a thickness of 25 μm. Then, it was dried in a hot air circulation oven at 80° C. for 6 minutes to evaporate the solvent to obtain a polyimide film and a resin film (dry film material) having a thickness of 50 μm on the polyimide film.

In Table 1, the numerical values in the columns of Examples 1 to 9 and Comparative Examples 1 to 3 represent the content (parts by weight) of each component. In addition, in Table 1, descriptions of "none" and "-" indicate that the corresponding ingredients are not contained. Hereinafter, the present invention will be described more specifically by means of examples, but they are not intended to limit the scope of the present invention, and are only used as illustrations.

The evaluation listed in Table 1 is carried out in the following way:

[Haze measurement]

According to the above method, using the resin compositions of Examples 1 to 9 and Comparative Examples 1 to 3, coated on a releaseable support material (polyimide film) and dried at 80°C, the resin composition with The dry film material of the resin film with a thickness of 50 μm is torn off the support material to obtain the corresponding resin film, and the haze of these resin films is measured by using Nippon Denshoku COH 5500 according to the ASTM D1003 standard.

[Storage modulus of elasticity]

According to the above method, use the resin compositions of Examples 1 to 9 and Comparative Examples 1 to 3 to prepare corresponding dry film materials (which have a resin film with a thickness of 50 μm), and then carry out the process in a hot air circulation oven at 180°C for two hours. Heat curing to obtain a cured resin film with a support material as the bottom layer. After peeling off the cured resin film from the support material (polyimide film), cut it into a 50mm×3mm strip test piece, use a thermodynamic analyzer (Perkin Elmer DMA8000) under nitrogen, at 1Hz The frequency and heating rate are 5°C/min. Measurements were made within the range of 50°C to 300°C to determine the storage elastic modulus at 50°C and 200°C in Table 1.

[Evaluation of CTE]

According to the above method, use the resin compositions of Examples 1 to 9 and Comparative Examples 1 to 3 to prepare corresponding dry film materials (which have a resin film with a thickness of 50 μm), and then carry out the process in a hot air circulation oven at 180°C for two hours. Heat curing to obtain a cured resin film with a support material as the bottom layer. After the cured resin film was peeled off from the support (polyimide film), it was cut into strip-shaped test pieces of 50 mm×3 mm, and measured using a thermomechanical analyzer (Perkin Elmer TMA4000). Under nitrogen, under the measurement condition of heating rate of 5°C/min, within the temperature range of 50°C to 300°C, CTEα1 (0~50°C) was measured twice consecutively.

[chemical resistance (acid resistance)]

According to the above method, use the resin compositions of Examples 1 to 9 and Comparative Examples 1 to 3 to prepare corresponding dry film materials (which have a resin film with a thickness of 50 μm), and then carry out the process in a hot air circulation oven at 180°C for two hours. Heat curing to obtain a cured resin film with a support material as the bottom layer. After the cured resin film is peeled off from the support material (polyimide film), it is cut into strip test pieces of 50 mm x 50 mm, immersed in a sulfuric acid aqueous solution with a concentration of 10% by mass for 30 minutes at room temperature, and then Wash with water. After washing with water, it was checked whether there was any change on the surface of the membrane.

The evaluation criteria of alkali resistance are as follows.

O: There is no change in the film surface.

X: The surface of the film is slightly fogged or cracked.

[Td1]

According to the above method, use the resin compositions of Examples 1 to 9 and Comparative Examples 1 to 3 to prepare corresponding dry film materials (which have a resin film with a thickness of 50 μm), and then carry out the process in a hot air circulation oven at 180°C for two hours. Heat curing to obtain a cured resin film with a support material as the bottom layer. After the cured resin film was peeled off from the support material (polyimide film), it was cut to make a sample. Using a thermogravimetric analyzer (Perkin Elmer TGA4000), the sample was tested in the range of 50°C to 1000°C under nitrogen with a heating rate of 10°C/min. The results are shown in Table 1, where , Td1 is 1% thermal decomposition temperature, that is, the temperature at which the sample loses 1% of its weight.

The manufacturers of the ingredients used in Table 1 are as follows:

Component A: polymers synthesized in Synthesis Examples and Synthesis Comparative Examples.

Component B: YX4000 (manufactured by Mitsubishi Chemical); HP7200 (manufactured by DIC); and GE24 (manufactured by CVC).

Component C: LA-1356 (manufactured by DIC); and HPC-6000-85T (manufactured by DIC)

Component D: MEK-ST-40 (Nissan Chemical), which is silicon dioxide accounting for 40% of methyl ethyl ketone, particle size [BET] is 10~15nm).

Hardening accelerator: DMAP (Sigma-Aldrich)

Silane coupling agent: KBM-403 (manufactured by Shin-Etsu Chemical)

As shown in Table 1, compared with Comparative Examples 1-3, Examples 1-9 have lower haze, which proves that the polymer of the present invention helps to improve the haze of the resin film. Compared with Comparative Examples 1 and 2, Examples 1-9 exhibit lower coefficients of thermal expansion (CTE). Although comparative example 3 can also obtain a low coefficient of thermal expansion, its haze is obviously inferior to that of the present invention, so it cannot be used as an adhesive film.

It can be seen from the above that the film formed by the resin composition of the present invention has at least the following advantages: (1) low haze; (2) low thermal expansion coefficient; (3) good chemical resistance; (4) good thermal stability.

The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention. It should be pointed out that for those of ordinary skill in the art, some improvements can be made without departing from the technical principle of the present invention. and modifications, these improvements and modifications should also be considered as the protection scope of the present invention.

Claims (13)

A kind of polymer, its weight average molecular weight is 1,000～100,000, and it comprises the structure shown in formula (I):

Wherein, X is each independently a tetravalent organic group; Y is each independently a divalent residue of a dicarboxylic acid; E is each independently -NH- or -O-; A and B are each independently a divalent organic group, And at least one of A and B is a group shown in the following formula (II) or a group shown in formula (III):

Wherein, q is any integer from 0 to 3; each Q is independently a single bond, -CH ₂ -, -C ₂ H ₂ -, -C ₂ H ₄ -, -C ₃ H ₆ -, -C ₄ H ₈ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ , -O-, -CO-, -CONH-, -COO-, -S(O) ₂ -, -S(O) ₂ NH-, -CH ₂ CO-, -CH ₂ CONH- or fluorenylidene; and R ¹ is each independently R ² or -L-Ph-R ² , wherein L is each independently a single bond, -CH ₂ -, -C ₂ H ₂ -, -C ₂ H ₄ -, -C ₃ H ₆ -, -C ₄ H ₈ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ , -O- , -CO-, -CONH-, -COO-, -S(O) ₂ -, -S(O) ₂ NH-, -CH ₂ CO- or -CH ₂ CONH-; each R ² is independently -CONH ₂ ; m and n are each independently any integer from 0 to 300, but m and n are not 0 at the same time; and the polymer comprises at least one group shown in the formula (II) or the group shown in the formula (III) group, and the polymer meets at least one of the following conditions (i) and (ii): (i) the hydroxyl value is 50~500 (KOH) mg/g; (ii) the amine value is 50~ 500 (HClO ₄ ) mg/g. Polymer as claimed in item 1, wherein the group shown in the formula (II) is selected from:

, wherein Q, R ¹ , R ² and L are as defined in Claim 1. The polymer as described in claim 2, wherein the group represented by the formula (II) is selected from:

, wherein R ¹ and R ² are as defined in Claim 1. The polymer as described in claim 1, wherein the molar percentage of the group represented by the formula (II) or formula (III) is 10-100% of the total repeating unit. A resin composition comprising: the polymer as claimed in claim 1; an epoxy resin; a hardener; and an inorganic filler. The resin composition according to claim 5, further comprising at least one of a hardening accelerator and a silane coupling agent. The resin composition according to claim 5, wherein the haze of the formed film is 50 or less. The resin composition according to claim 5, wherein the cured film formed has a storage elastic modulus of 1.8 or more at 50°C. A resin film formed from the resin composition as described in claim 5. An adhesive film comprising: a base material; and the resin film according to claim 9, which is disposed on the base material. The adhesive film according to claim 10, wherein the resin film has a haze of 50 or less. A printed circuit board comprising an insulating layer, and the insulating layer is a cured product of the resin film according to claim 9. A semiconductor device comprising the printed circuit board as claimed in claim 12.