TW202126725A - Polyimide precursor composition and use thereof - Google Patents

Abstract

The present invention provides a polyimide precursor composition includes an amic acid ester oligomer having the structure of formula (1): wherein G, X, Y, R, Rx, P1, m1, m2 and m3 are those as defined in the specification. A dry film containing the polyimide precursor composition and a polyimide film or laminate prepared from the polyimide precursor composition are also provided.

Description

Polyimide precursor composition and application thereof

The present invention relates to a polyimide (PI) precursor composition, a dry film containing the polyimide precursor composition, and a polyimide prepared from the polyimide precursor composition Imine film.

Polyimide has always been the first choice for high-performance polymer materials due to its excellent thermal stability and good mechanical, electrical and chemical properties. Polyimide plays a key role in applications such as the integrated circuit industry, electronic assembly, enameled wire, printed circuit boards, sensing components, separation membranes and structural materials.

As far as printed circuit boards are concerned, in recent years, as electronic products emphasize lightness, thinness, shortness, and smallness, the size of various electronic components must also be made smaller and smaller. Under this development trend, they are light, thin and resistant to high temperatures. Flexible printed circuit boards (FPC), which have characteristics and can be mass-produced, have more room for development. Flexible printed circuit boards are widely used in products such as 3C products, optical lens modules, LCD modules and solar cells. At present, popular electronic products such as mobile phones, liquid crystal displays and organic light-emitting diodes can all be seen in flexible printed circuit boards. Of the trail.

Flexible printed circuit boards are made by arranging circuits and other electronic components on flexible substrates. Compared with printed circuit boards using traditional silicon substrates or glass substrates, they have better flexibility, so they can also be called flexible boards. A coverlay is usually added on the surface of the soft board, which can be used as an insulating protective layer to protect the copper circuit on the surface of the soft board and increase the circuit's bending resistance. Therefore, the coverlay material must have better chemical resistance , Heat resistance, dimensional stability, insulation properties and bending resistance.

Although polyimine meets the aforementioned characteristics, polyimine is generally made by heating polyimine precursors (such as amide ester oligomers) at high temperatures to fully polymerize and cyclize into polyimides with sufficient molecular weight. Imine, so that the obtained polyimine has good thermal stability and good mechanical, electrical and chemical properties. However, when applied to cover film, because the flexible printed circuit board has already configured circuits and various electronic components, it cannot withstand high-temperature manufacturing processes, which limits the application of traditional polyimide materials in cover film elements; in addition, generally polyimide Imine has excellent mechanical properties (such as rigidity), which often leads to poor bending resistance, causing the cover film to break after bending, causing corrosion and oxidation of the exposed copper.

In view of this, there is a continuing need in the technical field to develop polyimide materials that are suitable for low-temperature cyclization processes and can obtain good physical properties.

(1) 其中 X具有式(1-a)

之重複單元， Y具有式(1-b)

之重複單元， m₁ 是0至100的整數； m₂ 是1至100的整數； m₃ 是1至100的整數； R_x 各自獨立為H、C₁ -C₁₄ 烷基、或含乙烯系不飽和基的基團； R各自獨立為C₁ -C₁₄ 烷基、C₆ -C₁₄ 芳基或芳烷基、或含乙烯系不飽和基的基團； G各自獨立為四價有機基團； P₁ 各自獨立為二價有機基團，其包含選自(i)式(A)之二價矽氧烷有機基團、(ii)C₂ -C₁₄ 伸烷基團、(iii)式(B)之二價基團及其組合所組成之群之基團：

(A)

(B) 其中R₆ '各自獨立為H、C₁ -C₄ 烷基、或苯基，k可相同或不相同且為大於0的整數，r為大於0的整數，且f為大於0的整數； P₂ 各自獨立為二價有機基團，其限制條件為P₂ 不是(i)式(A)之二價矽氧烷有機基團、(ii)C₂ -C₁₄ 伸烷基團或(iii)式(B)之二價基團；且 其中以P₁ 和P₂ 基團之總莫耳數計，(i)、(ii)、(iii)及其組合之總含量為0.5莫耳%至30莫耳%。One object of the present invention is to provide a novel polyimide precursor composition, which comprises the amide ester oligomer of formula (1):

(1) where X has formula (1-a)

The repeating unit, Y has the formula (1-b)

M ₁ is an integer from 0 to 100; m ₂ is an integer from 1 to 100; m ₃ is an integer from 1 to 100; R _{x is} each independently H, C ₁ -C ₁₄ alkyl, or vinyl-containing An unsaturated group; R each independently is a C ₁ -C ₁₄ alkyl group, a C ₆ -C ₁₄ aryl group or an aralkyl group, or a group containing an ethylenically unsaturated group; G each independently is a tetravalent organic group Group; P _{1 is} each independently a divalent organic group, which includes a divalent siloxane organic group selected from the group consisting of (i) formula (A), (ii) C ₂ -C ₁₄ alkylene group, (iii) The group consisting of the divalent group of formula (B) and its combination:

(A)

(B) where R ₆ 'is each independently H, C ₁ -C ₄ alkyl, or phenyl, k may be the same or different and is an integer greater than 0, r is an integer greater than 0, and f is greater than 0 Integer; P _{2 is} each independently a divalent organic group, and its restriction is that P ₂ is not (i) a divalent siloxane organic group of formula (A), (ii) a C ₂ -C ₁₄ alkylene group or (iii) The divalent group of formula (B); and the total content of (i), (ii), (iii) and their combination is 0.5 moles based on the total moles of _{P 1} and P _{2 groups} Ear% to 30 mol%.

Another object of the present invention is to provide a dry film containing the above-mentioned polyimide precursor composition.

Another object of the present invention is to provide a polyimide film prepared from the above polyimide precursor composition.

In order to make the above objectives, technical features, and advantages of the present invention more obvious and understandable, some specific embodiments are described below in detail.

In order to facilitate the understanding of the disclosure stated in this article, a number of terms are defined below.

The term "T _g " is an abbreviation for glass transition temperature.

The term "CTE" is an abbreviation for coefficient of thermal expansion.

The term "about" means the acceptable error of a specific value as measured by a person familiar with the art, and the range of error depends on how the value is measured or measured.

In the present invention, the term "alkyl" refers to a saturated linear or branched hydrocarbon group, preferably having 1 to 14 carbon atoms, more preferably 1 to 6 or 1 to 4 carbon atoms; examples thereof include (but Not limited to): methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, pentyl, hexyl and similar groups. Unless otherwise specified, in the present invention, "alkyl" may be substituted or unsubstituted. Substituents such as, but not limited to: halo, hydroxy, -CN, C ₆ -C ₁₄ aryl group, a 5- or 6-membered nitrogen-containing heterocyclic group.

In the present invention, the term "alkenyl" refers to an unsaturated linear or branched hydrocarbon group having at least one carbon-carbon double bond, preferably having 2 to 10 carbon atoms, more preferably having 3 to 8 carbon atoms; Examples include (but are not limited to): vinyl, propenyl, methpropenyl, isopropenyl, pentenyl, hexenyl, heptenyl, 1-propenyl, 2-butenyl, 2-methyl Group-2-butenyl and similar groups.

In the present invention, the term "aryl" refers to, for example, a monocyclic, bicyclic or tricyclic aromatic carbocyclic group containing 6 to 14 carbon atoms, examples of which include (but are not limited to): phenyl, indenyl, naphthalene Group, fluorenyl, anthracenyl, phenanthryl and similar groups. Unless otherwise specified, in the present invention, "aryl" may be substituted or unsubstituted. Substituents include, but are not limited to: halogen, hydroxyl, -NO ₂ , alkyl and the like.

In the present invention, the term "aralkyl" refers to a group composed of an aryl group and an alkyl group, and the group can be bonded to other groups via an alkyl group or an aryl group; examples thereof include (but are not limited to) : 3-methylphenyl, 4-methylphenyl and similar groups. Unless otherwise specified, the "aryl" part and the "alkyl" part may be substituted or unsubstituted, and the substituents are as described above.

In the present invention, the term "haloalkyl" refers to an alkyl substituted by halogen, where "halogen" means fluorine, chlorine, bromine or iodine.

In the present invention, the term "alkoxy" refers to -O-alkyl, examples of which include (but are not limited to): methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, Isobutoxy, tertiary butoxy, pentoxy, hexyloxy and similar groups. Unless otherwise specified, the "alkyl" moiety may be substituted or unsubstituted, and the substituents are as described above.

In the present invention, the term "heterocyclic group" refers to a saturated or partially saturated (for example, with the prefix dihydro, trihydro, tetrahydro, Hexahydro and other names) or unsaturated 3 to 14 membered ring group, preferably 4 to 10 membered ring group, more preferably 5 or 6 membered ring group; preferably 1 to 4 heteroatoms, more preferably 1 to 3 heteroatoms. The heterocyclic group may be a monocyclic, bicyclic, or tricyclic ring system, which includes a fused ring (for example, a fused ring formed with another heterocyclic ring or another aromatic carbocyclic ring). Unless otherwise specified, in the present invention, the "heterocyclic group" may be substituted or unsubstituted. Substituents include, but are not limited to, halogen, hydroxyl, oxo, alkyl, hydroxyalkyl, -NO ₂ and the like.

In the present invention, the term "nitrogen-containing heterocyclic group" refers to a 3- to 14-membered heterocyclic group in which at least one ring carbon atom is replaced by a N atom, preferably a 4- to 10-membered nitrogen-containing heterocyclic group, more preferably 5 or 6-membered nitrogen-containing heterocyclic group. Examples include but are not limited to: pyrrolyl, imidazolyl, pyrazolyl, pyrimidinyl, thiazolyl, pyridyl, indolyl , Isoindolyl, benzimidazolyl, benzothiazolyl, quinolyl, isoquinolyl, etc. Unless otherwise specified, in the present invention, the "nitrogen-containing heterocyclic group" may be substituted or unsubstituted. Substituents include, but are not limited to, halogen, hydroxyl, oxo, alkyl, hydroxyalkyl, -NO ₂ and the like.

In the present invention, the term "oxygen-containing heterocyclic group" refers to a 3- to 14-membered heterocyclic group in which at least one ring carbon atom is replaced by an O atom, preferably a 4- to 10-membered oxygen-containing heterocyclic group, more preferably A 5- or 6-membered oxygen-containing heterocyclic group. Examples thereof include, but are not limited to: furanyl, pyranyl, tetrahydrofuranyl, tetrahydropyranyl, dibenzopyranyl and the like. Unless otherwise specified, in the present invention, the "oxygen-containing heterocyclic group" may be substituted or unsubstituted. Substituents include, but are not limited to, halogen, hydroxyl, oxo, alkyl, hydroxyalkyl, -NO ₂ and the like.

Each aspect and each embodiment of the present invention disclosed in this specification can be individually combined with all other aspects and embodiments of the present invention, covering all possible combinations.

(1) 其中： X具有式(1-a)

之重複單元， Y具有式(1-b)

之重複單元， m₁ 是0至100的整數，例如，0、1、2、3、4、5、7、10、20、30、40、50、60、70、80、90或100； m₂ 是1至100的整數，例如，1、2、3、4、5、7、10、20、30、40、50、60、70、80、90或100； m₃ 是1至100的整數，例如，1、2、3、4、5、7、10、20、30、40、50、60、70、80、90或100； R_x 各自獨立為H、C₁ -C₁₄ 烷基、或含乙烯系不飽和基的基團； R各自獨立為C₁ -C₁₄ 烷基、C₆ -C₁₄ 芳基或芳烷基、或含乙烯系不飽和基的基團； G各自獨立為四價有機基團； P₁ 各自獨立為二價有機基團，其包含(i)式(A)之二價矽氧烷有機基團、(ii)C₂ -C₁₄ 伸烷基團、(iii)式(B)之基團及其組合：

(A)

(B) 其中R₆ '各自獨立為H、C₁ -C₄ 烷基、或苯基，k可相同或不相同且為大於0的整數，r為大於0的整數，且f為大於0的整數； P₂ 各自獨立為二價有機基團，其限制條件為P₂ 不是(i)式(A)之二價矽氧烷有機基團、(ii)C₂ -C₁₄ 伸烷基團或(iii)式(B)之二價基團；且 其中以P₁ 和P₂ 基團之總莫耳數計，(i)、(ii)、(iii)及其組合之總含量為0.5莫耳%至20莫耳%，例如：0.5莫耳%、1莫耳%、3莫耳%、5莫耳%、8莫耳%、10莫耳%、12莫耳%、15莫耳%、18莫耳%、20莫耳%，較佳為1莫耳%至15莫耳%，更佳為2莫耳%至10莫耳%。若(i)、(ii)、(iii)及其組合之總含量過高，將導致所得聚醯亞胺過軟、機械性質不佳、耐熱性較差、熱膨脹係數過高；若(i)、(ii)、(iii)及其組合之總含量過低，將導致所得聚醯亞胺過硬、耐彎折性不佳、玻璃轉換溫度過高、熱膨脹係數過低等等。 I. Polyimide precursor composition 1. The urethane oligomer of formula (1)

(1) Where: X has the formula (1-a)

The repeating unit, Y has the formula (1-b)

M ₁ is an integer from 0 to 100, for example, 0, 1, 2, 3, 4, 5, 7, 10, 20, 30, 40, 50, 60, 70, 80, 90 or 100; m ₂ is an integer from 1 to 100, for example, 1, 2, 3, 4, 5, 7, 10, 20, 30, 40, 50, 60, 70, 80, 90 or 100; m ₃ is an integer from 1 to 100 , For example, 1, 2, 3, 4, 5, 7, 10 _{, 20} , 30, _{40, 50, 60, 70, 80, 90 or 100; R x is} each independently H, C ₁ -C 14 alkyl, Or an ethylenically unsaturated group-containing group; R is each independently a C ₁ -C ₁₄ alkyl group, a C ₆ -C ₁₄ aryl group or an aralkyl group, or an ethylenically unsaturated group-containing group; G is each independently A tetravalent organic group; P _{1 is} each independently a divalent organic group, which includes (i) a divalent siloxane organic group of formula (A), (ii) a C ₂ -C ₁₄ alkylene group, ( iii) The group and combination of formula (B):

(A)

(B) where R ₆ 'is each independently H, C ₁ -C ₄ alkyl, or phenyl, k may be the same or different and is an integer greater than 0, r is an integer greater than 0, and f is greater than 0 Integer; P _{2 is} each independently a divalent organic group, and its restriction is that P ₂ is not (i) a divalent siloxane organic group of formula (A), (ii) a C ₂ -C ₁₄ alkylene group or (iii) The divalent group of formula (B); and the total content of (i), (ii), (iii) and their combination is 0.5 moles based on the total moles of _{P 1} and P _{2 groups} Ear% to 20 mol%, for example: 0.5 mol%, 1 mol%, 3 mol%, 5 mol%, 8 mol%, 10 mol%, 12 mol%, 15 mol%, 18 mol%, 20 mol%, preferably 1 mol% to 15 mol%, more preferably 2 mol% to 10 mol%. If the total content of (i), (ii), (iii) and their combination is too high, the resulting polyimide will be too soft, poor mechanical properties, poor heat resistance, and too high thermal expansion coefficient; if (i), If the total content of (ii), (iii) and their combination is too low, the resulting polyimide will be too hard, poorly resistant to bending, too high glass transition temperature, too low thermal expansion coefficient and so on.

The above-mentioned "C ₁ -C ₁₄ alkyl group" may be linear or branched, preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, n-propyl Pentyl, isopentyl, hexyl, heptyl, or octyl.

(C) 其中R₇ 係伸苯基、C₁ -C₈ 伸烷基、C₂ -C₈ 伸烯基、C₃ -C₈ 伸環烷基、C₁ -C₈ 羥伸烷基或

，其中n'為1至4之整數，且R₈ 係H或C₁ -C₄ 烷基。The above-mentioned "ethylenically unsaturated group-containing group" refers to a group containing at least one C=C bond, which can undergo a crosslinking reaction when exposed to light. _{When R or R x} in the oligomer structure is selected as a group with an ethylenically unsaturated group, the oligomer can be made photosensitive. The "group containing an ethylenically unsaturated group" is preferably selected from the following group: vinyl, propenyl, methpropenyl, n-butenyl, isobutenyl, vinyl phenyl, propenyl phenyl, propylene Oxymethyl, propyleneoxyethyl, propyleneoxypropyl, propyleneoxybutyl, propyleneoxypentyl, propyleneoxyhexyl, methacryloxymethyl, methacryloxyethyl, Methacryloxypropyl, methacryloxybutyl, methacryloxypentyl, methacryloxyhexyl and groups with the following formula (C):

(C) wherein R ₇ is phenylene, C ₁ -C ₈ alkylene, C ₂ -C ₈ alkenylene, C ₃ -C ₈ cycloalkylene, C ₁ -C ₈ hydroxyalkylene or

, Where n'is an integer from 1 to 4, and R ₈ is H or C ₁ -C ₄ alkyl.

According to some embodiments of the present invention, m ₁ is an integer from 0 to 50, m ₂ is an integer from 1 to 50, and m ₃ is an integer from 1 to 50.

According to some embodiments of the present invention _{, the sum of m 1} , m ₂ , and m ₃ is 2 to 100, for example, it can be 2, 3, 4, 5, 6, 8, 10, 15, 20, 25, 30, 40 , 50, 60, 70, 80, 90 or 100, preferably 3-50, more preferably 8-25. If _{the sum of m 1} , m ₂ , and m ₃ is too large, the molecular weight of the obtained urethane oligomer will be too large, which will have the disadvantages of high viscosity and poor solubility, which is not conducive to the development process.

According to some embodiments of the present invention, the ratio of the sum of _{m 1} and m _{3 to m 2} ranges from about 0.1 to about 0.5, preferably from about 0.2 to about 0.4, more preferably from about 0.25 to about 0.33.

According to some embodiments of the present invention, k is an integer between 2 and 5, and may be 2, 3, 4, or 5, for example.

According to some embodiments of the present invention, r is an integer between 1 and 60, for example, it can be 1, 2, 5, 10, 12, 20, 30, 40, 50 or 60, preferably between 1 and 12. Integer.

According to some embodiments of the present invention, f is an integer between 1 and 60, for example, it can be 1, 2, 3, 5, 10, 12, 20, 30, 40, 50, or 60, preferably 1 to 12. Integer between.

、

、

、

、及其組合； 其中r之定義如本文先前所述。According to some embodiments of the present invention, the group of formula (A) of (i) is selected from the group consisting of:

,

,

,

, And combinations thereof; wherein r is defined as previously described herein.

或

。According to some embodiments of the present invention, the group of formula (A) of (i) is preferably:

or

.

、

、

、

、

、及其組合。According to some embodiments of the present invention, the C ₂ -C ₁₄ alkylene group of (ii) is selected from the group consisting of:

,

,

,

,

, And combinations thereof.

、

、

、及其組合。According to some embodiments of the present invention, the group of formula (B) in (iii) is preferably:

,

,

, And combinations thereof.

According to some embodiments of the present invention, P ₁ further includes a divalent aromatic group or a divalent heterocyclic group independently of each other.

、及其組合；其中， R₉ 各自獨立為H、C₁ -C₄ 烷基、C₁ -C₄ 全氟烷基、C₁ -C₄ 烷氧基、鹵素、-OH、-COOH、-NH₂ 、或-SH； a與b各自獨立為0至4之整數；及 R₁₀ 為共價鍵或選自由以下所組成之群組之基團： -O-、-S-、-CH₂ -、-S(O)₂ -、

、

、-C(CF₃ )₂ -、-C(O)-、-C(CH₃ )₂ -、-CONH-、

、

、

及

；其中， c與d各自獨立為0至20之整數； R₉ 與a如前所述；及 R₁₂ 為-S(O)₂ -、-C(O)-、共價鍵、C₁ -C₄ 烷基或C₁ -C₄ 全氟烷基。The aforementioned divalent aromatic group or divalent heterocyclic group is preferably selected from the group consisting of:

, And combinations thereof; wherein R _{9 is} each independently H, C ₁ -C ₄ alkyl, C ₁ -C ₄ perfluoroalkyl, C ₁ -C ₄ alkoxy, halogen, -OH, -COOH,- NH ₂ , or -SH; a and b are each independently an integer from 0 to 4; and R ₁₀ is a covalent bond or a group selected from the group consisting of: -O-, -S-, -CH ₂ -, -S(O) ₂ -,

,

, -C(CF ₃ ) ₂ -, -C(O)-, -C(CH ₃ ) ₂ -, -CONH-,

,

,

and

; Wherein, c and d are each independently an integer from 0 to 20; R ₉ and a are as described above; and R ₁₂ is -S(O) ₂ -, -C(O)-, covalent bond, C _1- C ₄ alkyl or C ₁ -C ₄ perfluoroalkyl.

；其中， a各自獨立為0至4之整數；及 Z各自獨立為H、甲基、三氟甲基或鹵素。The aforementioned divalent aromatic group or divalent heterocyclic group is more preferably selected from the group consisting of:

; Wherein, a is each independently an integer from 0 to 4; and Z is each independently H, methyl, trifluoromethyl or halogen.

According to other embodiments of the present invention, the divalent aromatic group or the divalent heterocyclic group is selected from the group consisting of:

According to some embodiments of the present invention, P ₂ includes each independent divalent aromatic group or divalent heterocyclic group, and the definition and implementation aspects of the divalent aromatic group or divalent heterocyclic group are as described herein As mentioned earlier.

、

及

； 其中X各自獨立為H、鹵素、C₁ -C₄ 全氟烷基或C₁ -C₄ 烷基，且A及B每次出現係各自獨立為共價鍵、未經取代或經一或多個選自羥基及C₁ -C₄ 烷基之基團取代的C₁ -C₄ 伸烷基、C₁ -C₄ 全氟伸烷基、C₁ -C₄ 伸烷氧基、伸矽烷基、-O-、-S-、-C(O)-、-OC(O)-、-S(O)₂ -、-C(=O)O-(C₁ -C₄ 伸烷基)-OC(=O)-、-CONH-、苯、聯苯或

，其中K為-O-、-S(O)₂ -、C₁ -C₄ 伸烷基或C₁ -C₄ 全氟伸烷基，且其中r為1至60之整數，例如可為1、2、5、10、12、20、30、40、50或60，較佳為1至12之間的整數。According to some embodiments of the present invention, the G system is selected from the group consisting of:

,

and

; Wherein X is each independently H, halogen, C ₁ -C ₄ perfluoroalkyl or C ₁ -C ₄ alkyl, and each occurrence of A and B is each independently a covalent bond, unsubstituted or through one or _{C 1} -C ₄ alkylene, C ₁ -C ₄ perfluoroalkylene, C ₁ -C ₄ alkoxy, silylene substituted by a plurality of groups selected from hydroxyl and C ₁ -C _{4 alkyl} Base, -O-, -S-, -C(O)-, -OC(O)-, -S(O) ₂ -, -C(=O)O-(C ₁ -C ₄ alkylene) -OC(=O)-, -CONH-, benzene, biphenyl or

, Wherein K is -O-, -S(O) ₂ -, C ₁ -C ₄ alkylene or C ₁ -C ₄ perfluoroalkylene, and wherein r is an integer from 1 to 60, for example, 1 , 2, 5, 10, 12, 20, 30, 40, 50 or 60, preferably an integer between 1-12.

； 其中Z各自獨立為H、甲基、三氟甲基或鹵素。G is preferably selected from the group consisting of:

; Wherein Z is each independently H, methyl, trifluoromethyl or halogen.

、

、

、

、

、

、

、

、

、

、

、

、

、

、及其組合。According to some embodiments of the present invention, each R is independently selected from the following group:

,

,

,

,

,

,

,

,

,

,

,

,

,

, And combinations thereof.

、

、

、

、

。According to some embodiments of the present invention, R _{x is} each independently H, methyl, ethyl, propyl, butyl, 2-hydroxypropyl methacrylate, ethyl methacrylate, ethyl acrylate , Propenyl, methpropenyl, n-butenyl or isobutenyl. R _{x is} preferably each independently H or selected from the group consisting of:

,

,

,

,

.

。The amide acid ester oligomer of formula (1) of the present invention is in block form, that is, as shown in formula (1), X and Y units are present in the oligomer in a block manner and are formed in sequence

.

(b)   於步驟(a)產物中添加具式H₂ N-P₁ -NH₂ 之二胺化合物，形成式(5)之中間物且留下些許H₂ N-P₁ -NH₂ 於步驟(c)中進行反應；

(5) (c)    於步驟(b)產物中添加過量具式(3)之二酸酐，形成式(6)之中間物；

(6) 各式(6)之中間物可能具有不同之m₁ ，m₁ 定義如上所述。 (d)   於步驟(c)產物中添加具式H₂ N-P₂ -NH₂ 之二胺化合物，形成式(7)之聚醯亞胺前驅物；

(7) 於此步驟中，所加入之H₂ N-P₂ -NH₂ 二胺化合物會與來自步驟(c)的剩餘二酸酐反應生成包含P₂ 基團之聚合嵌段，隨後步驟(c)所得之含有P₁ 基團之中間物接枝於該聚合嵌段之兩側（由於兩端可能含有不同數目的重複單元，故標示為m₁ 及m₃ 作區別，m₃ 至少為1）； (e)  視情況添加帶有可感光聚合基團(R*)之單體或可酯化酸根之單體，例如乙烯醚類丙烯酸酯(vinyl ether acrylate)或甲醯胺縮醛類(formamide acetal)，進行反應，將部分或全部-OH取代為-OR_x 。The polymerization method of the urethane oligomer of formula (1) of the present invention can be any suitable method well known to those having ordinary knowledge in the technical field of the present invention. For example (but not limited to this), in some embodiments of the present invention, the polymerization method of the amide ester oligomer-based block copolymer of the present invention may include the following steps: (a) A dianhydride of the following formula (3) and a compound having a hydroxyl group (R-OH) undergo an isomolar reaction in a solvent to form an intermediate of the following formula (4);

_{(b) Add a diamine compound of formula H 2} NP ₁ -NH _{2 to} the product of step (a) to form an intermediate of formula (5) and leave some H ₂ NP ₁ -NH ₂ in step (c) React

(5) (c) Add excess dianhydride of formula (3) to the product of step (b) to form an intermediate of formula (6);

(6) The intermediates of formula (6) may have different m ₁ , and m _{1 is} defined as described above. _{(d) Adding a diamine compound of formula H 2} NP ₂ -NH _{2 to} the product of step (c) to form a polyimide precursor of formula (7);

(7) In this step, the added H ₂ NP ₂ -NH ₂ diamine compound will react with the remaining dianhydride from step (c) to form a _{polymer block containing P 2} groups, and then the result of step (c) The intermediates containing P ₁ groups are grafted on both sides of the polymer block (because the two ends may contain different numbers of repeating units, they are marked as m ₁ and m ₃ for distinction, and m _{3 is} at least 1); ( e) Optionally add monomers with photopolymerizable groups (R*) or monomers that can be esterified, such as vinyl ether acrylate or formamide acetal , Proceed with the reaction, and replace part or all of -OH with -OR _x .

The amide acid ester oligomer of formula (1) of the present invention has two or more blocks with different structures. The inventors of the present invention found that by introducing two different blocks composed of specific units, the amide acid The ester oligomer is cyclized and polymerized at a lower temperature (for example, ≤260 ^o C), and the obtained polyimide not only maintains good rigidity, heat resistance and deformation resistance, but also can be flexed. Without being limited by theory, the inventor believes that this may be due to the following reasons: First, the block composed of X units (also called soft segment) contains bases of (i), (ii), (iii) or a combination thereof. Tuan Xian believes that it has a lower T _g , therefore, through the soft segment softening at a lower temperature, the fluidity of the amide ester oligomer can be improved, and the collision probability with the diamine compound can be increased to promote the reaction, thereby A polyimide with sufficient molecular weight can be formed at a lower temperature, and the soft segment also provides better toughness, elongation and bending resistance of the polyimide; in addition, it is believed that the soft segment makes the polyimide The reason for its good toughness and bending resistance. Second, the block composed of Y units (also called hard segment) is believed to have a high T _g , so it can provide polyimide with good rigidity, heat resistance and deformation resistance. According to the examples and comparative examples of the present invention, the random copolymer compound cannot exhibit the above-mentioned characteristics.

2. Diamine compound In addition to the amide ester oligomer of formula (1), the polyimide precursor composition of the present invention may additionally contain a diamine compound, which can be combined with the amide compound of formula (1) The acid ester oligomer is polymerized to increase the molecular weight, and the type can be any suitable diamine compound known to those with ordinary knowledge in the technical field of the present invention.

、或

； R₁ 為H、未經取代或經一或多個選自C₁ -C₈ 烷基及C₁ -C₈ 鹵烷基之基團取代之C₆ -C₁₄ 芳基、含氮雜環基、C₄ -C₁₀ 環烷基、未經取代之C₁ -C₈ 烷基或C₁ -C₈ 烷氧基或經一或多個選自C₆ -C₁₄ 芳基、含氮雜環基、-S-R₄ 、

及-CN之基團取代之C₁ -C₈ 烷基或C₁ -C₈ 烷氧基、C₁ -C₈ 鹵烷基、C₁ -C₈ 鹵烷氧基、或-NR₅ R₆ ； R₁₃ 為

、

、-OR₁₅ 或C₁ -C₁₀ 烷氧基； R₄ 、R₅ 及R₆ 可相同或不相同且各自獨立為H、未經取代或經一或多個C₆ -C₁₄ 芳基取代之C₁ -C₈ 烷基或C₁ -C₈ 烷氧基、未經取代或經一或多個選自C₁ -C₈ 烷基及–NO₂ 之基團取代之C₆ -C₁₄ 芳基或C₆ -C₁₄ 芳氧基、或含氮雜環基； R₁₄ 為(甲基)丙烯醯氧基； R₁₅ 為C₄ -C₁₀ 環烷基或含氧雜環基；及 t為1至20的整數，較佳為1至10的整數，更佳為1至5的整數。According to some embodiments of the present invention, the diamine compound has a structure of the following formula (2): D-NH-P'-NH-D (2) wherein P'is each independently a divalent organic group, for example, as previously defined herein A divalent aromatic group or a divalent heterocyclic group; D is each independently H, unsubstituted or C substituted with one or more groups selected from C ₆ -C ₁₄ aryl and nitrogen-containing heterocyclic groups ₁ -C ₈ alkyl, unsubstituted or substituted by one or more groups selected from C ₁ -C ₈ alkyl, C ₁ -C ₈ hydroxyalkyl, pendant oxy and -NO ₂ Cyclic group, unsubstituted or nitrogen-containing heterocyclic group substituted with one or more groups selected from pendant oxy groups, C ₁ -C ₈ alkyl groups and -NO _2,

,or

; R ₁ is H, unsubstituted or substituted by one or more groups selected from C ₁ -C ₈ alkyl and C ₁ -C ₈ haloalkyl, C ₆ -C ₁₄ aryl, nitrogen-containing heterocycle Group, C ₄ -C ₁₀ cycloalkyl, unsubstituted C ₁ -C ₈ alkyl or C ₁ -C ₈ alkoxy or one or more selected from C ₆ -C ₁₄ aryl, nitrogen-containing hetero Ring group, -SR ₄ ,

_{C 1} -C ₈ alkyl or C ₁ -C ₈ alkoxy, C ₁ -C ₈ haloalkyl, C ₁ -C ₈ haloalkoxy, or -NR ₅ R ₆ substituted by the group of -CN ; R ₁₃ is

,

, -OR ₁₅ or C ₁ -C ₁₀ alkoxy; R ₄ , R ₅ and R ₆ may be the same or different and are each independently H, unsubstituted or substituted with one or more C ₆ -C ₁₄ aryl groups C ₁ -C ₈ alkyl or C ₁ -C ₈ alkoxy, unsubstituted or C ₆ -C ₁₄ substituted with one or more groups selected from C ₁ -C ₈ alkyl and -NO ₂ Aryl or C ₆ -C ₁₄ aryloxy or nitrogen-containing heterocyclic group; R ₁₄ is (meth)acryloyloxy; R ₁₅ is C ₄ -C ₁₀ cycloalkyl or oxygen-containing heterocyclic group; and t is an integer from 1 to 20, preferably an integer from 1 to 10, more preferably an integer from 1 to 5.

In the polyimide precursor composition of the present invention, the ratio of the total moles of the amide ester oligomer of formula (1) to the total moles of the diamine compound is not particularly limited. For example, it can be adjusted It is in the range of 0.8:1 to 1.2:1, preferably in the range of 0.9:1 to 1.1:1.

According to some embodiments of the present invention, the terminal amine group of the diamine compound of formula (2) can be modified by using the group D which is not H to provide temporary protection and avoid the diamine compound of formula (2) React with dehydrating agent or the main chain of formula (1) amide acid ester oligomer. The modified diamine compound of formula (2) has lower reactivity at room temperature or even higher temperatures from 50°C to 90°C, so it will not interact with amide oligomers The main chain reaction on it can improve storage stability.

According to some embodiments of the present invention, the aforementioned group D for providing temporary protection can be removed by heating. In these embodiments, when the temperature is increased (for example, the temperature is increased to 90°C to 170°C). ), the group D will be removed and reduced to -NH ₂ , that is, a diamine compound of the _{formula NH 2} -P'-NH _{2 is formed.} Subsequently, the diamine compound can react with the reactive group (such as carboxylic acid group or ester group) possessed by the amide acid ester oligomer of formula (1) to form a higher molecular weight polymer to provide excellent thermal Polyimide with properties, mechanical properties and tensile properties.

According to some embodiments of the present invention, in addition to removing the group D by heating, it is also possible to add light to the composition according to the characteristics of the group D (for example, easy to remove in an acidic environment or easy to remove in an alkaline environment). Acid generator or photobase generator. The photoacid generator or photobase generator can separate acidic or basic compounds after exposure to light. Therefore, when a photoacid generator or a photobase generator is contained in the composition, an acidic or alkaline environment can be created by illumination, thereby removing the corresponding group D. The type and amount of photoacid generator or photobase generator are not particularly limited.

The method for preparing and using the modified diamine compound of formula (2), which can provide temporary protection, is as disclosed in US Patent Publication No. US 2018/0148541 A1, which is incorporated in this case by reference in its entirety.

3. Solvents and additives The polyimide precursor composition of the present invention further includes a solvent to facilitate the synthesis of the amide ester oligomer of formula (1) or the diamine compound of formula (2), or to increase the composition Leveling, making it easy to coat. The above-mentioned solvent can be any suitable solvent well known to those with ordinary knowledge in the field of the present invention, and the content thereof is not particularly limited.

、

、

及其混合物所組成之群組；其中： R₁ ''各自獨立為H、C₁ -C₂₀ 烷基、C₂ -C₂₀ 烯基或C₂ -C₂₀ 炔基； R₇ ''為H或C₁ -C₃ 烷基； R₂ ''為H、C₁ -C₁₅ 烷基或C₄ -C₈ 環烷基； R₃ ''及R₄ ''各自獨立為C₁ -C₁₀ 烷基，或R₃ ''及R₄ ''與其所連接之氮原子一起形成5至6員雜環； R₆ ''為C₁ -C₁₅ 烷基、C₂ -C₂₀ 烯基或C₄ -C₈ 環烷基。According to some embodiments of the present invention, the solvent is selected from: dimethyl sulfoxide, diethyl sulfoxide, tetrahydrofuran, dioxane, dioxolane, cyclopropylene glycol methyl ether, tetraethylene glycol dimethyl ether, γ-butyrolactone, xylene, toluene, hexamethyl phthalamide, propylene glycol methyl ether acetate,

,

,

And a group consisting of a mixture thereof; wherein: R ₁ '' is independently H, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl or C ₂ -C ₂₀ alkynyl; R ₇ '' is H Or C ₁ -C ₃ alkyl; R ₂ '' is H, C ₁ -C ₁₅ alkyl or C ₄ -C ₈ cycloalkyl; R ₃ '' and R ₄ '' are each independently C ₁ -C ₁₀ Alkyl group, or R _{3 ”} and R _4” together with the nitrogen atom to which they are connected, form a 5- to 6-membered heterocyclic ring; R _{6 ”} is C ₁ -C ₁₅ alkyl, C ₂ -C ₂₀ alkenyl or C ₄ -C ₈ cycloalkyl.

結構之溶劑之實例，包含但不限於：N,N-二甲基甲醯胺(N,N-dimethylformamide，DMF)、N,N-二乙基甲醯胺(N,N-diethylformamide，DEF)、N,N-二甲基乙醯胺(N,N-dimethylacetamide，DMAc)、N,N-二乙基乙醯胺(N,N-diethylacetamide，DEAc)、或N,N-二甲基癸醯胺(N,N-dimethylcapramide，DMC)。The above tools

Examples of structural solvents include but are not limited to: N,N-dimethylformamide (DMF), N,N-diethylformamide (DEF) , N,N-dimethylacetamide (N,N-dimethylacetamide, DMAc), N,N-diethylacetamide (N,N-diethylacetamide, DEAc), or N,N-dimethylacetamide N,N-dimethylcapramide (DMC).

結構之溶劑之實例，包含但不限於：N-甲基-2-吡咯烷酮(N-methyl-2-pyrrolidone，NMP)、N-乙烯基-2-吡咯烷酮(N-vinyl-2-pyrrolidone，NVP)、N-乙基-2-吡咯烷酮(N-ethyl-2-pyrrolidone，NEP)、或N-辛基-2-吡咯烷酮(N-octyl-2-pyrrolidone，NOP)。The above tools

Examples of structural solvents include but are not limited to: N-methyl-2-pyrrolidone (NMP), N-vinyl-2-pyrrolidone (NVP) , N-ethyl-2-pyrrolidone (N-ethyl-2-pyrrolidone, NEP), or N-octyl-2-pyrrolidone (N-octyl-2-pyrrolidone, NOP).

The polyimide precursor composition of the present invention may optionally contain a photoinitiator (for example, when applied to a photosensitive cover film or other processes requiring photosensitive polyimide). The above-mentioned photoinitiator is used to generate free radicals by light irradiation, and initiate the polymerization reaction through the transfer of free radicals. The photoinitiator suitable for the present invention is not particularly limited, for example, but not limited to, selected from the group consisting of benzophenone, benzophenone, 2-hydroxy-2-methyl-1-benzene Acetone, 2,2-Dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenylketone, 2,4,6-trimethylbenzyldiphenyl Phosphine oxides, oxime esters, and combinations thereof. The content of the photoinitiator can be adjusted by a person with ordinary knowledge in the technical field of the present invention through routine experiments. According to an embodiment of the present invention, the content of the photoinitiator is in the range of about 0.5 to about 5 parts by weight based on the total weight of the solid content of the composition.

The polyimide precursor composition of the present invention may optionally contain other additives known to those with ordinary knowledge in the technical field of the present invention that can be used to prepare polyimine, such as (but not limited to): pigments, leveling Agents, defoamers, coupling agents, dehydrating agents, thermal base generators, photo base generators, photo acid generators, copper adhesion promoters, closed ring promoters, catalysts, and co-initiators, etc. The content of the above-mentioned additives can also be adjusted by a person with ordinary knowledge in the technical field of the present invention through routine experiments.

The coupling agent that can be used in the present invention can be selected from the following group (but not limited to): 3-aminopropyltrimethoxysilane (APrTMOS), 3-triaminopropyltriethoxysilane (APrTEOS) ), 3-aminophenyltrimethoxysilane (APTMOS), 3-aminophenyltriethoxysilane (APTEOS) and combinations thereof.

The adhesion promoter that can be used in the present invention can be selected from the group consisting of (but not limited to) the following: imidazole, pyridine, triazole, and combinations thereof. When the adhesion promoter is present, the amount of the adhesion promoter is about 0.1 to about 2 parts by weight based on 100 parts by weight of the oligomer of formula (1).

、

、

、

、

、

、

、

、

、

、

Y^θ 、

Y^θ 、

Y^θ 、

Y^θ 、

Y^θ 、及其組合， 其中Y^θ 為陰離子基團。The thermal alkali generator that can be used in the present invention can be selected from the group consisting of:

,

,

,

,

,

,

,

,

,

,

Y ^θ ,

Y ^θ ,

Y ^θ ,

Y ^θ ,

Y ^θ , and combinations thereof, wherein Y ^θ is an anionic group.

4. Polyimine precursor composition The polyimine precursor composition of the present invention, based on the total weight of the polyimine precursor composition, of the formula (1) of the amide ester oligomer The content is about 5 wt% to about 95 wt%, preferably 10 wt% to about 60 wt%, and the remainder is diamine compound, solvent and/or additives.

The polyimide precursor composition of the present invention may be photosensitive or non-photosensitive, and is preferably a photosensitive polyimide precursor composition. The photosensitive polyimide precursor composition can be used to prepare a cover film through an exposure and development process.

According to some embodiments of the present invention, the photosensitive polyimine precursor composition of the present invention contains a photosensitive polyimine precursor composition, for example, the amide ester oligomer of formula (1) _{Add the R or R x} group of the ethylenically unsaturated group to the compound, or add a photoacid generator or a photobase generator for photosensitivity.

II. Dry film containing polyimine precursor composition The present invention also provides a dry film containing the aforementioned polyimine precursor composition.

The dry film of the present invention comprises a supporting substrate and a resin layer on the supporting substrate, wherein the resin layer comprises the aforementioned polyimide precursor composition.

The solvent content in the resin layer is at least 5wt%, at least 6wt%, at least 7wt%, or at least 10wt% based on the total weight of the resin layer, preferably between 15wt% and 70wt%, more preferably between 30wt% and 65wt% %, preferably between 40wt% and 60wt%. When the solvent content is too low, it may cause the precipitation of specific monomers, affect the exposure resolution (in the case of photosensitivity) and affect the subsequent bonding process. In severe cases, the bonding may not be possible; when the solvent content is too high, it may overflow Glue, affect the uniformity of film thickness, and have surface sticking problems. The types of the above-mentioned solvents are as previously described herein.

The above-mentioned supporting substrate may be any known to those having ordinary knowledge in the technical field of the present invention, such as glass or plastic. The above-mentioned plastic substrate is not particularly limited, and it is for example but not limited to: polyester resin, such as polyethylene terephthalate (PET) or polyethylene naphthalate (polyethylene naphthalate, PEN); polymethacrylate resin (polymethacrylate resin), such as polymethyl methacrylate (PMMA); polyimide resin (polyimide resin); polystyrene resin (polystyrene resin); polycycloolefin Polycycloolefin resin; polycycloolefin resin; polycarbonate resin; polyurethane resin; triacetate cellulose (TAC); or others mixture. Preferably it is polyethylene terephthalate, polymethyl methacrylate, polycycloolefin resin, cellulose triacetate or a mixture thereof, and more preferably polyethylene terephthalate. The thickness of the support substrate generally depends on the requirements of the desired electronic product, and it is preferably between about 16 μm and about 250 μm.

According to some embodiments of the present invention, the surface on which the support substrate is bonded to the resin layer has an average surface roughness (Ra) of 0 to 5 μm. The average surface roughness of the center line of the surface to be measured can be measured using a 3D interferometer or an atomic force microscope.

The dry film of the present invention can be prepared by, for example, the following steps: (1) Prepare a polyimide precursor composition, including the amide ester oligomer of formula (1), the diamine of formula (2) and solvents/additives as needed; (2) Coating the polyimide precursor composition of step (1) on the supporting substrate to form a dry film semi-finished product including the supporting substrate and the resin layer; (3) Send the dry film semi-finished product to the baking oven, heat and dry to remove the solvent, thereby adjusting the solvent content in the resin layer; and (4) If necessary, apply a protective film on the resin layer.

The solvent in the above step (1) can be added during the preparation of the amide oligomer of the formula (1) or the diamine of the formula (2) to facilitate the synthesis of the above compounds; or after the preparation is completed, to adjust The operability of the polyimide precursor composition makes it convenient for subsequent coating.

When the dry film is laminated to a substrate such as a flexible printed circuit board, during the lamination process, gas often remains between the resin layer of the dry film and the substrate to be laminated, and bubbles are left after the lamination. The existence of air bubbles will make the quality of the dry film abnormal and affect the performance of the circuit board. Therefore, vacuum laminating equipment is generally used to exhaust air during lamination.

However, due to the high cost of vacuum laminating equipment, and the laminating operation can only adopt a sheet by sheet operation mode, which cannot achieve a roll-to-roll production mode. Therefore, in a preferred embodiment of the present invention, in step (3), the heating time and temperature can be controlled (for example, at a suitable temperature between 80°C and 250°C for 30 seconds). Heat and dry until 10 minutes), adjust the solvent content in the dry film semi-finished product, for example, make the solvent exist in an amount of at least 5wt%, at least 6wt%, at least 7wt% or at least 10wt% (based on the total weight of the resin layer), In this way, the dry film has a bubble-dissolving effect. After the pressing process, high pressure (4~10kgf/cm ² ) can be applied as needed to allow the air between the substrate and the dry film to dissolve into the dry film. Among the solvents, it can solve the air bubble problem generated by the dry film in the flexible printed circuit board pressing process, without the use of vacuum film pressing equipment. In addition, the dry film of the present invention has water absorption, and its properties are relatively stable even in the presence of water, and the surface is not sticky, has good transfer ability, and the polyimide obtained by curing has good physical properties. It can also be applied to wet pressing.

The protective film of the above step (4), for example, but not limited to: polyester resin, such as polyethylene terephthalate or polyethylene naphthalate; polymethacrylate resin, such as polymethyl methacrylate ; Polyimide resin; Polystyrene resin; Polycyclic olefin resin; Polyolefin resin; Polycarbonate resin; Polyurethane resin; Triacetate cellulose; or their mixture. Preferably it is polyethylene terephthalate, polymethyl methacrylate, polycycloolefin resin, cellulose triacetate or a mixture thereof, and more preferably polyethylene terephthalate.

The dry film of the present invention is suitable for printed circuit boards or used on the surface of semiconductor packaging. As a covering film, it has insulation properties and can protect circuits from oxidation and soldering short circuits. The dry film of the present invention is also suitable for use as a dielectric layer of a semiconductor.

According to a preferred embodiment of the present invention, the dry film of the present invention contains a photosensitive polyimide precursor composition. The dry film of the present invention containing photosensitive polyimide precursor composition has the characteristics of high resolution, fast developing speed, resistance to electroplating, high temperature resistance and high humidity resistance, and is suitable for use as semiconductors, active passives, and optoelectronics. The insulating material or cover film of the component.

In addition, since the urethane oligomer of formula (1) has two or more blocks with different structures (ie, soft segment and hard segment), the flow can be improved by the soft segment with lower heating. In turn, the collision probability of the amide acid ester oligomer and the diamine compound is increased to carry out the cyclization polymerization reaction, so that the polyimide with sufficient molecular weight ^{can be formed at a lower temperature (for example, ≤260 o C)} . Therefore, the dry film of the present invention is particularly suitable for covering films used in flexible printed circuit boards, which can effectively solve the problems of the prior art, and the obtained covering film has good toughness, elongation, bending resistance, rigidity, heat resistance and resistance. Deformability and other advantages.

III. Polyimide film The present invention also provides a polyimide film made from the aforementioned polyimide precursor composition.

According to aspects of some embodiments of the present invention, the polyimide film of the present invention has a glass transition temperature lower than 340 ^o C, preferably between 250 ^o C to 340 ^o C, such as, but not limited to 250 ^o C, 260 ^o C, 270 ^o C, 280 ^o C, 290 ^o C, 300 ^o C, 310 ^o C, 320 ^o C, 330 ^o C or 340 ^o C.

According to some embodiments of the present invention, the X unit includes polymerized units derived from long-chain diamine monomers and aromatic diamine monomers.

(2-a)、

(2-b)、

(2-c)、或其組合， 其中R₆ '各自獨立為H、C₁ -C₄ 烷基、或苯基，k可相同或不相同且為大於0的整數，r為大於0的整數，R₂ '為C₂ -C₁₄ 伸烷基團，且f為大於0的整數。k、r及f之實施態樣係如本文先前所述。The aforementioned long-chain diamine single system refers to a diamine monomer with at least four adjacent atoms in the main chain and no aromatic group on the main chain, including the following:

(2-a),

(2-b),

(2-c), or a combination thereof, wherein R ₆ ′ is each independently H, C ₁ -C ₄ alkyl, or phenyl, k may be the same or different and is an integer greater than 0, and r is an integer greater than 0 , R ₂ ′ is a C ₂ -C ₁₄ alkylene group, and f is an integer greater than 0. The implementation aspects of k, r and f are as previously described herein.

According to some embodiments of the present invention, the content of the aforementioned long-chain diamine monomers, based on the total moles of diamine monomers contained in the X unit, is about 2 mol% to about 100 mol%, for example, About 2 mol%, about 4 mol%, about 5 mol%, about 8 mol%, about 10 mol%, about 20 mol%, about 30 mol%, about 40 mol%, about 50 Mol%, about 60 mol%, about 70 mol%, about 80 mol%, about 90 mol% or about 100 mol%, preferably about 4 mol% to about 60 mol%, more Preferably, it is about 5 mol% to about 40 mol%.

或其組合， 其中a、b、c、d、R₉ 及R₁₀ 之定義及實施態樣係如本文先前所述。According to some embodiments of the present invention, the Y unit includes polymerized units derived from the following monomers:

Or a combination thereof, wherein the definitions and implementation aspects of a, b, c, d, R ₉ and R _{10 are as previously described herein.}

According to a preferred embodiment of the present invention, the Y unit does not include polymerized units derived from long-chain diamine monomers.

About 2ppm / ^o C to embodiments according to some aspects, polyimide film of the present invention is approximately 55ppm / ^o C the coefficient of thermal expansion (the CTE of), for example of about 2ppm / ^o C, from about 5ppm / ^o C, from about 10ppm / ^o C, from about 20ppm / ^o C, from about 30ppm / ^o C, from about 40ppm / ^o C, from about 50ppm / ^o C or from about 55ppm / ^o C the coefficient of thermal expansion.

The preparation of the polyimide film of the present invention can directly coat the above-mentioned polyimide precursor composition on the substrate, after baking, remove part of the solvent and carry out exposure and development, and then heat to remove the remaining solvent and make The diamine compound reacts with the amide acid ester oligomer to polymerize to form a polyimide to prepare a polyimide film.

There are no special restrictions on the heating temperature and time mentioned above, and can be adjusted as needed. The heating step can be performed in a single stage or in multiple stages. In an embodiment of the present invention, a two-stage heating method is used. The first stage is ^{continuous heating at a temperature range of 70 to 170 o} C for 5 to 100 minutes, and the second stage is heated at a temperature range of 170 to 260 ^o C. Continue heating for 60 to 240 minutes.

The polyimide film of the present invention can be applied to electronic components, wherein the electronic components are flexible printed circuit boards, semiconductor components, active and passive components, display components or touch panels.

In general, the polyimide precursor composition of the present invention has the characteristics of low-temperature cyclization, and the cyclized polyimide has good physical properties, tortuosity resistance, mechanical strength, heat resistance, and deformation resistance. It is suitable for use as a cover film and a dielectric layer.

The following examples illustrate the implementation of the present invention and explain the technical features of the present invention, and are not intended to limit the scope of protection of the present invention. Any change or equivalence arrangement that can be easily accomplished by a person familiar with this technology belongs to the scope of the present invention, and the scope of protection of the rights of the present invention shall be subject to the scope of the attached patent application.

P-PAM：

Examples The abbreviations mentioned in the following examples are defined as follows: H-PAM:

P-PAM:

Preparation Example 1 (1.11 mol% H-PAM) 5.88 grams (0.02 mol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride (3,3',4,4'-biphenyltetracarboxylic dianhydride, BPDA for short) was dissolved in 160 grams of NMP, and 2.32 grams (0.02 mol) of 2-hydroxyethyl acrylate (HEA for short) was slowly dripped in, and the reaction was stirred at 50°C for 2 hours. Thereafter, 0.497 g (0.002 mol) of H-PAM and 11.61 g (0.058 mol) of 4,4'-diaminodiphenyl ether (4,4'-oxydianiline, ODA) were added to the solution , Stir and react at 50°C for 1 hour. Subsequently, 52.96 g (0.18 mol) of BPDA was added and the reaction was stirred at 50°C for 1 hour. Then add 12.97 g (0.12 mol) of p-phenylenediamine (pPDA). After it is completely dissolved, stir and react at 50°C for 6 hours to obtain the polymer precursor glue PAA- 01, the solid content is about 30wt%.

Preparation Example 2 (3.33 mol% H-PAM) Dissolve 5.88 g (0.02 mol) of BPDA in 160 g of NMP, slowly drop 2.32 g (0.02 mol) of HEA, and stir at 50°C for reaction 2 Hours. Thereafter, 1.491 g (0.006 mol) of H-PAM and 10.81 g (0.054 mol) of ODA were added to the solution, and the reaction was stirred at 50°C for 1 hour. Subsequently, 52.96 g (0.18 mol) of BPDA was added and the reaction was stirred at 50°C for 1 hour. Then add 12.97 g (0.12 mol) of pPDA, and after it is completely dissolved, the reaction is stirred at 50°C for 6 hours to obtain the polymer precursor glue PAA-02 with a solid content of about 30wt%.

Preparation Example 3 (5.56 mol% H-PAM) Dissolve 5.88 g (0.02 mol) of BPDA in 160 g of NMP, slowly drop 2.32 g (0.02 mol) of HEA, and stir at 50°C for reaction 2. Hours. Thereafter, 2.485 g (0.01 mol) of H-PAM and 10.01 g (0.05 mol) of ODA were added to the solution, and the reaction was stirred at 50° C. for 1 hour. Subsequently, 52.96 g (0.18 mol) of BPDA was added and the reaction was stirred at 50°C for 1 hour. Then add 12.97 g (0.12 mol) of pPDA, and after it is completely dissolved, the reaction is stirred at 50°C for 6 hours to obtain the polymer precursor glue PAA-03 with a solid content of about 30wt%.

Preparation Example 4 (8.89 mol% H- PAM) Dissolve 5.88 g (0.02 mol) of BPDA in 160 g of NMP, slowly drop 2.32 g (0.02 mol) of HEA, and stir at 50°C for reaction 2. Hours. Thereafter, 3.976 g (0.016 mol) of H-PAM and 8.81 g (0.044 mol) of ODA were added to the solution, and the reaction was stirred at 50°C for 1 hour. Subsequently, 52.96 g (0.18 mol) of BPDA was added and the reaction was stirred at 50°C for 1 hour. Then add 12.97 g (0.12 mol) of pPDA, and after it is completely dissolved, stir and react at 50°C for 6 hours to obtain the polymer precursor glue PAA-04 with a solid content of about 30wt%.

Preparation Example 5 (11.1 mol% H-PAM) Dissolve 5.88 g (0.02 mol) of BPDA in 160 g of NMP, slowly drop 2.32 g (0.02 mol) of HEA, and stir at 50°C for reaction 2 Hours. Thereafter, 4.97 g (0.02 mol) of H-PAM and 8.00 g (0.04 mol) of ODA were added to the solution, and the reaction was stirred at 50°C for 1 hour. Subsequently, 52.96 g (0.18 mol) of BPDA was added and the reaction was stirred at 50°C for 1 hour. Then add 12.97 g (0.12 mol) of pPDA, and after it is completely dissolved, the reaction is stirred at 50°C for 6 hours to obtain the polymer precursor glue PAA-05 with a solid content of about 30wt%.

Preparation Example 6 (15.6 mol% H-PAM) Dissolve 5.88 g (0.02 mol) of BPDA in 160 g of NMP, slowly drop 2.32 g (0.02 mol) of HEA, and stir at 50°C for reaction 2 Hours. Thereafter, 6.96 g (0.028 mol) of H-PAM and 6.41 g (0.032 mol) of ODA were added to the solution, and the reaction was stirred at 50°C for 1 hour. Subsequently, 52.96 g (0.18 mol) of BPDA was added and the reaction was stirred at 50°C for 1 hour. Then add 12.97 g (0.12 mol) of pPDA, and after it is completely dissolved, the reaction is stirred at 50°C for 6 hours to obtain the polymer precursor glue PAA-06 with a solid content of about 30wt%.

Preparation Example 7 (3.33 mol% P-PAM) Dissolve 5.88 g (0.02 mol) of BPDA in 160 g of NMP, slowly drop 2.32 g (0.02 mol) of HEA, and stir at 50°C for reaction 2 Hours. Thereafter, 3.00 g (0.006 mol) of P-PAM and 10.81 g (0.054 mol) of ODA were added to the solution, and the reaction was stirred at 50°C for 1 hour. Subsequently, 52.96 g (0.18 mol) of BPDA was added and the reaction was stirred at 50°C for 1 hour. Then add 12.97 g (0.12 mol) of pPDA, and after it is completely dissolved, the reaction is stirred at 50°C for 6 hours to obtain the polymer precursor glue PAA-7 with a solid content of about 30wt%.

同製備例4的方法，唯將H-PAM改為0.53g(0.006莫耳)的1,4-丁二胺(1,4-diaminobutane)，其餘條件皆相同，反應後可得聚合物前驅物之膠液PAA-8，固含量約30wt%。 Preparation Example 8 (3.33 mol% 1,4 -butanediamine )

Same as Preparation Example 4, except that H-PAM is changed to 0.53g (0.006 mol) of 1,4-diaminobutane, and the other conditions are the same. After the reaction, the polymer precursor can be obtained. The glue liquid PAA-8, the solid content is about 30wt%.

同製備例4的方法，唯將H-PAM改為0.70g(0.006莫耳)的1,6-己二胺(1,6-diaminohexane)，其餘條件皆相同，反應後可得聚合物前驅物之膠液PAA-9，固含量約30wt%。 Preparation Example 9 (3.33 mol% 1,6- hexanediamine )

Same as Preparation Example 4, except that H-PAM is changed to 0.70g (0.006 mol) of 1,6-diaminohexane, other conditions are the same, and the polymer precursor can be obtained after the reaction The glue liquid PAA-9, the solid content is about 30wt%.

(EO-1) 同製備例4的方法，唯將H-PAM改為0.89g(0.006莫耳)的1,8-二胺基-3,6-二氧辛烷(1,8-diamino-3,6-dioxaoctane)，其餘條件皆相同，反應後可得聚合物前驅物之膠液PAA-10，固含量約30wt%。 Preparation Example 10 (3.33 mol% 1,8 -diamino- 3,6- dioxoctane (EO-1))

(EO-1) Same as Preparation Example 4, except that H-PAM is changed to 0.89g (0.006 mol) of 1,8-diamino-3,6-dioxoctane (1,8-diamino- 3,6-dioxaoctane), other conditions are the same, after the reaction, the polymer precursor glue PAA-10 can be obtained, and the solid content is about 30wt%.

(EO-2) 同製備例4的方法，唯將H-PAM改為1.15g(0.006莫耳)的雙[2-(2-氨基乙氧基)乙基]醚(bis[2-(2-aminoethoxy)ethyl]ether)，其餘條件皆相同，反應後可得聚合物前驅物之膠液PAA-11，固含量約30wt%。 Preparation Example 11 (3.33 mol% bis [2-(2 -aminoethoxy ) ethyl ] ether (EO-2))

(EO-2) Same as Preparation Example 4, except that H-PAM was changed to 1.15g (0.006 mol) of bis[2-(2-aminoethoxy)ethyl]ether (bis[2-(2 -aminoethoxy)ethyl]ether), the other conditions are the same, after the reaction, the glue solution PAA-11 of the polymer precursor can be obtained, and the solid content is about 30wt%.

Preparation Example 12 ( without ingredients (i) , (ii) or (iii) ) Dissolve 5.88 g (0.02 mol) of BPDA in 160 g of NMP, slowly drip 2.32 g (0.02 mol) of HEA, The reaction was stirred at 50°C for 2 hours. Thereafter, 12.01 g (0.06 mol) of ODA was added to the solution, and the reaction was stirred at 50°C for 1 hour. Subsequently, 52.96 g (0.18 mol) of BPDA was added and the reaction was stirred at 50°C for 1 hour. Then add 12.97 g (0.12 mol) of pPDA, and after it is completely dissolved, the reaction is stirred at 50°C for 6 hours to obtain the polymer precursor glue PAA-12 with a solid content of about 30wt%.

Preparation Example 13 (0.22 mol% H-PAM) Dissolve 5.88 g (0.02 mol) of BPDA in 160 g of NMP, slowly drop 2.32 g (0.02 mol) of HEA, and stir at 50°C for reaction 2 Hours. Thereafter, 0.099 g (0.0004 mol) of H-PAM and 11.93 g (0.0596 mol) of ODA were added to the solution, and the reaction was stirred at 50° C. for 1 hour. Subsequently, 52.96 g (0.18 mol) of BPDA was added and the reaction was stirred at 50°C for 1 hour. Then add 12.97 g (0.12 mol) of pPDA, and after it is completely dissolved, stir and react at 50°C for 6 hours to obtain the polymer precursor glue PAA-13 with a solid content of about 30wt%.

Preparation Example 14 (21.1 mol% H-PAM) Dissolve 5.88 g (0.02 mol) of BPDA in 160 g of NMP, slowly drip 2.32 g (0.02 mol) of HEA, and stir at 50°C for reaction 2 Hours. Thereafter, 9.443 g (0.038 mol) of H-PAM and 4.4 g (0.022 mol) of ODA were added to the solution, and the reaction was stirred at 50°C for 1 hour. Subsequently, 52.96 g (0.18 mol) of BPDA was added and the reaction was stirred at 50°C for 1 hour. Then add 12.97 g (0.12 mol) of pPDA, and after it is completely dissolved, the reaction is stirred at 50°C for 6 hours to obtain the polymer precursor glue PAA-14 with a solid content of about 30wt%.

Preparation Example 15 (3.33 mol% H-PAM random oligomer ) Dissolve 5.88 g (0.02 mol) of BPDA in 160 g of NMP, and slowly drop 2.32 g (0.02 mol) of HEA at 50° The reaction was stirred at C for 2 hours. Thereafter, 1.496 g (0.006 mol) of H-PAM and 10.81 g (0.054 mol) of ODA, 12.97 g (0.12 mol) of pPDA and 52.96 g (0.18 mol) of BPDA were added to the solution, After it is completely dissolved, the reaction is stirred at 50°C for 6 hours to obtain the polymer precursor glue PAA-15 with a solid content of about 30wt%.

Preparation Example 16 (11.1 mol% H-PAM random oligomer ) Dissolve 5.88 g (0.02 mol) of BPDA in 160 g of NMP, and slowly drop 2.32 g (0.02 mol) of HEA at 50° The reaction was stirred at C for 2 hours. Thereafter, 4.97 g (0.02 mol) of H-PAM and 8.00 g (0.04 mol) of ODA, 12.97 g (0.12 mol) of pPDA and 52.96 g (0.18 mol) of BPDA were added to the solution, After it is completely dissolved, it is stirred and reacted at 50°C for 6 hours to obtain the polymer precursor glue PAA-16 with a solid content of about 30wt%.

， P’ 為

) 將10.814克(0.1莫耳)的pPDA加至甲苯溶劑中，在攪拌的過程中緩慢加入42.006克(0.2莫耳)的三氟醋酸酐(trifluoroacetic acid anhydride，簡稱TFAA)，在50ºC下攪拌反應1個小時後即可得DA-1，分子量300.16g/mol。 < Preparation of Diamine Compound > Preparation Example DA-1 ( Preparation of diamine of formula (2) , D is

, P 'is

) Add 10.814 g (0.1 mol) of pPDA to the toluene solvent, slowly add 42.006 g (0.2 mol) of trifluoroacetic acid anhydride (TFAA) during the stirring process, and stir at 50ºC for reaction DA-1 can be obtained after 1 hour, with a molecular weight of 300.16g/mol.

， P’ 為

) 將10.814克(0.1莫耳)的pPDA放置於反應器中，在攪拌的過程中加入43.650克(0.2莫耳)的二碳酸二叔丁酯(di-tert-butyl dicarbonate，簡稱Boc2O)，在50ºC下攪拌反應1個小時後即可得DA-2，分子量308.38g/mol。 Preparation Example DA-2 ( Preparation of diamine of formula (2) , D is

, P 'is

) Place 10.814 grams (0.1 mol) of pPDA in the reactor, and add 43.650 grams (0.2 mol) of di-tert-butyl dicarbonate (Boc2O) during the stirring process. After stirring and reacting at 50ºC for 1 hour, DA-2 can be obtained, with a molecular weight of 308.38g/mol.

< Polyimine precursor composition and dry film preparation > Example 1-1 (1.11 mol% H-PAM) Take 100 grams of glue PAA-01, add 6 grams of diamine DA-1, mix well and then add 30 grams of solvent N,N-dimethylcapramide (DMC) and 2 grams of photoinitiator (Ciba, Irgacure OXE-01) to prepare polyimide precursor composition PAA -C1. The polyimide precursor composition PAA-C1 prepared above was uniformly coated on a smooth PET film (Mitsubishi Plastic, R310) with a doctor blade, and baked in a hot air circulation oven at 95°C for 5 minutes to obtain polyimide Amine precursor composition dry film DF-1 (the film thickness is about 40 μm, the solvent content is about 50 wt%).

Example 1-2 (3.33 mol% H-PAM) is the same as the method of Example 1-1, except that the glue PAA-01 is changed to PAA-02 to prepare the polyimide precursor composition PAA-C2 and polyimide A dry film of the imine precursor composition DF-2 (the film thickness is about 40 μm, and the solvent content is about 50 wt%).

Example 1-3 (5.56 mol% H-PAM) is the same as that of Example 1-1, except that the glue PAA-01 is changed to PAA-03 to prepare the polyimide precursor composition PAA-C3 and polyimide A dry film of the imine precursor composition DF-3 (the film thickness is about 40 μm, and the solvent content is about 50 wt%).

Example 1-4 (8.89 mol% H- PAM ) The same method as in Example 1-1, except that the glue PAA-01 was changed to PAA-04, the polyimide precursor composition PAA-C4 and polyimide were prepared. A dry film of the imine precursor composition DF-4 (the film thickness is about 40 μm, and the solvent content is about 50 wt%).

Example 1-5 (11.11mol% H-PAM) is the same as Example 1-1, except that the glue PAA-01 is changed to PAA-05 to prepare the polyimide precursor composition PAA-C5 and polyimide The dry film of the imine precursor composition is DF-5 (the film thickness is about 40 μm, and the solvent content is about 50 wt%).

Example 1-6 (15.6 mol% H-PAM) is the same as the method of Example 1-1, except that the glue PAA-01 is changed to PAA-06 to prepare the polyimide precursor composition PAA-C6 and polyimide The dry film of the imine precursor composition is DF-6 (the film thickness is about 40 μm, and the solvent content is about 50 wt%).

Example 1-7 (3.33 mol% P-PAM) is the same as the method of Example 1-1, except that the glue PAA-01 is changed to PAA-7 to prepare the polyimide precursor composition PAA-C7 and polyimide The dry film of the imine precursor composition is DF-7 (the film thickness is about 40 μm, and the solvent content is about 50 wt%).

Example 1-8 (3.33 mol% 1,4 -butanediamine ) is the same as the method of Example 1, except that the glue PAA-01 is changed to PAA-8 to prepare the polyimide precursor composition PAA-C8 And polyimide precursor composition dry film DF-8 (the film thickness is about 40μm, the solvent content is about 50wt%).

Example 1-9 (3.33 mol% 1,6 -hexamethylenediamine ) is the same as Example 1-1, except that the glue PAA-01 is changed to PAA-9 to prepare the polyimide precursor composition PAA -C9 and polyimide precursor composition dry film DF-9 (the film thickness is about 40μm, the solvent content is about 50wt%).

Example 1-10 (3.33 mol% 1,8 -diamino- 3,6- dioxoctane (EO-1)) is the same as the method of Example 1-1, except that the glue PAA-01 is changed to PAA -10, prepared polyimide precursor composition PAA-C10 and polyimide precursor composition dry film DF-10 (the film thickness is about 40 μm, the solvent content is about 50 wt%).

Example 1-11 (3.33 mol% bis [2-(2 -aminoethoxy ) ethyl ] ether (EO-2)) is the same as the method of Example 1-1, except that the glue PAA-01 is changed to PAA -11, the polyimide precursor composition PAA-C11 and the polyimide precursor composition dry film DF-11 (the film thickness is about 40 μm, the solvent content is about 50 wt%) are prepared.

Comparative Examples 1-12 (no (i), (ii) or (iii) component) of the same method of Example 1-1 embodiment, only the glue to PAA-01 PAA-12, to prepare polyimide precursor Composition PAA-C12 and polyimide precursor composition dry film DF-12 (the film thickness is about 40μm, the solvent content is about 50wt%).

Comparative Example 1-13 (0.22 mol% H-PAM) was the same as the method of Example 1-1, except that the glue PAA-01 was changed to PAA-13 to obtain the polyimide precursor composition PAA-C13 and polyimide The dry film of the imine precursor composition is DF-13 (the film thickness is about 40 μm, and the solvent content is about 50 wt%).

Comparative Example 1-14 (21.1 mol% H-PAM) was the same as the method of Example 1-1, except that the glue PAA-01 was changed to PAA-14 to obtain the polyimide precursor composition PAA-C14 and polyimide The dry film of the imine precursor composition is DF-14 (the film thickness is about 40 μm, and the solvent content is about 50 wt%).

Comparative Example 1-15 (3.33 mol% H-PAM random oligomer ) was the same as the method of Example 1-1, except that the glue PAA-01 was changed to PAA-15 to prepare the polyimide precursor composition PAA-C15 and polyimide precursor composition dry film DF-15 (the film thickness is about 40μm, the solvent content is about 50wt%).

Comparative Example 1-16 (11.1 mol% H-PAM random oligomer ) was the same as the method of Example 1-1, except that the glue solution PAA-01 was changed to PAA-16 to prepare a polyimide precursor composition PAA-C16 and polyimide precursor composition dry film DF-16 (the film thickness is about 40μm, the solvent content is about 50wt%).

Example 1-17 (3.33 mol% H-PAM) is the same as the method of Example 1-4, except that the diamine DA-1 is changed to 6.16 grams of diamine DA-2 to prepare the polyimide precursor composition PAA -C17 and polyimide precursor composition dry film DF-17 (the film thickness is about 40μm, the solvent content is about 50wt%).

< Preparation of polyimide film > The dry film of the example and the comparative example is used on the surface of the resin layer and the flexible copper foil substrate (manufactured by Xinyang Co., Ltd., L/S=1/0.5mm & 0.5/1mm) ) Perform wet pressing, and then use a UV exposure machine to expose about 200-600mJ/cm ² to remove the PET film on the dry film; then use an oven to bake at a temperature of 70-90°C for 30 minutes, and then Pattern development was performed _{with a K 2} CO ₃ aqueous solution with a concentration of 1 wt%. Finally, it is baked in a nitrogen oven: the first stage is raised from room temperature to 170°C within 35 minutes, and fixed at 170°C for 60 minutes; the second stage is 170°C to 260°C, and Fixed baking at 260°C for 120 minutes to prepare a polyimide film coated on a copper foil substrate.

Test method Glass transition temperature (T _g ) measurement: the polyimide film coated on the copper foil substrate is etched and the copper foil substrate is removed to obtain the polyimide film. A dynamic mechanical analyzer (DMA, TA Q400 instrument of Texas Instruments) was used to measure the T _g data of the polyimide film after removing the copper foil substrate. The measurement range is 0 to 500°C, and the heating rate is 10°C/min.

Coefficient of Thermal Expansion (CTE) measurement: Use a thermomechanical analyzer (TMA, TA Q400 instrument of Texas Instruments) to measure the thermal expansion coefficient of the polyimide film after removing the copper foil substrate. The measurement range is 0 to 500°C, and the heating rate is 10°C/min.

Tensile strength measurement: Tensile strength is based on the IPC-TM-650 (2.4.18.3) method, using the universal tensile machine (instron-3342) to measure the polyimide after removing the copper foil substrate The tensile strength of the film.

Elongation test: elongation is based on the IPC-TM-650 (2.4.18.3) method, using the universal tensile machine (instron-3342) to measure the elongation of the polyimide film after removing the copper foil substrate .

Bending test: FIG. 1 is a schematic diagram of a copper foil substrate coated with a polyimide film. From bottom to top, the substrate 10, the copper circuit 20, and the cover film 30 are shown in sequence. The dashed line is the place that is easy to break during bending. Perform a bending test along the cut surface of the copper wire and the polyimide layer (that is, the position of the dotted line shown in Figure 1), bend it 180 degrees and bend it repeatedly until it is observed with an optical microscope, and it is found that the copper wire is exposed. It means that the polyimide layer is cracked, and the number of bending is recorded.

Thermal cracking test: _{Measure the T d5%} data of the polyimide film after removing the copper foil substrate with a thermogravimetric analyzer (TMA, TA Q5000 instrument of Texas Instruments). The measurement range is 0 to 600°C, and the heating rate is 10°C/min.

Flame resistance test: Use the flammability UL94 standard to test the flame resistance of the polyimide film after removing the copper foil substrate, and mark it with UL94 standard flame retardant grade (from low to high): VTM-2, VTM-1, VTM-0 Flame resistance.

< Test results > The related test results of each embodiment and comparative example are shown in Table 1 to Table 4: Table 1 Example 1-1 Example 1-2 Example 1-3 Example 1-4 Example 1-5 (i)+(ii)+(iii)/(P1+P2) 1.11 mol% H-PAM 3.33 mol% H-PAM 5.56 mol% H-PAM 8.89 mol% H-PAM 11.1 mol% H-PAM T _g ( ^o C) 333.8 310.0 292.3 275.6 262.14 CTE (ppm/ ^o C) 9.22 11.55 15.86 28.01 40.48 Tensile strength (MPa) 210.56 198.32 187.22 177.36 153.21 Elongation(%) 21.67 23.67 28.15 32.5 38.99 Bend test 120 times 134 times 157 times 169 times 180 times T _d 5% ( ^o C) 531 562 555 534 545 Flame resistance rating VTM-0 VTM-0 VTM-0 VTM-0 VTM-0 Table 2 Example 1-6 Example 1-7 Example 1-8 Example 1-9 Example 1-10 (i)+(ii)+(iii)/(P1+P2) 15.6 mol% H-PAM 3.33 mol% P-PAM 3.33 mol% 1,4-butanediamine 3.33 mol% 1,6-hexanediamine 3.33 mol% EO-1 T _g ( ^o C) 255.61 280.39 285.09 284.88 287.43 CTE (ppm/ ^o C) 51.37 11.77 13.02 12.89 13.64 Tensile strength (MPa) 142.54 200.21 205.11 198.54 196.37 Elongation(%) 44.14 24.02 25.54 25.87 24.65 Bend test 192 times 138 times 129 times 135 times 140 times T _d 5% ( ^o C) 539 558 559 555 560 Flame resistance rating VTM-0 VTM-0 VTM-0 VTM-0 VTM-0 table 3 Example 1-11 Comparative example 1-12 Comparative example 1-13 Comparative example 1-14 Comparative example 1-15 (i)+(ii)+(iii)/ (P1+P2) 3.33 mol% EO-2 0 0.22 mol% H-PAM 21.1 mol% H-PAM 3.33 mol% Random H-PAM T _g ( ^o C) 286.33 360 350.2 248.97 352.1 CTE (ppm/ ^o C) 13.55 5.4 5.8 58.87 27.07 Tensile strength (MPa) 196.64 246.05 221.01 142.54 192.25 Elongation(%) 25.21 15.09 17.03 52.36 25.03 Bend test 139 times 1 time 1 time 199 times 5 times T _d 5% ( ^o C) 561 544 555 511 533 Flame resistance rating VTM-0 VTM-0 VTM-0 VTM-1 VTM-0 Table 4 Comparative example 1-16 Example 1-17 (i)+(ii)+(iii)/ (P1+P2) 11.1 mol% Random H-PAM 3.33 mol% H-PAM (DA-2) T _g ( ^o C) 349.8 271.23 CTE (ppm/ ^o C) 38.42 26.01 Tensile strength (MPa) 189.71 178.88 Elongation(%) 28.12 36.66 Bend test 6 times 166 times T _d 5% ( ^o C) 548 532 Flame resistance rating VTM-0 VTM-0

It can be seen from the results that P _{1 of} Examples 1-1 to 1-11 and 1-17 contains a divalent siloxane organic group selected from the group consisting of (i) formula (A), and (ii) C ₂ -C ₁₄ alkylene Group, (iii) a group consisting of a divalent group of formula (B) and a combination thereof, and _{based on the total number of moles of P 1} and P ₂ groups, its content accounts for 0.5 mole% to 20 mol%; these polyimide precursor compositions can be ^{polymerized and cyclized into polyimine at a temperature of ≤260 o} C. The prepared polyimine has excellent bending resistance and maintains The comparative examples have comparable rigidity, elongation, heat resistance, deformation resistance and other properties.

In contrast, in Comparative Examples 1-12 to 1-16, the total content of (i), (ii), and (iii) contained in them is insufficient or too high, or they are random oligomers, and the resulting polyamide The amine film cannot meet the requirements: 1. The total content of (i), (ii) and (iii) in Comparative Examples 1-12 and 1-13 is insufficient, resulting in the obtained polyimide film being hard and resistant to bending Poor performance, the glass transition temperature is as high as 350 ^o C or more, and the coefficient of thermal expansion is too low. 2. The total content of (i), (ii), and (iii) in Comparative Examples 1-14 is too high, resulting in the resulting polyimide film being softer, and the resulting polyimide film being too soft and poor in mechanical properties (resistant to Low tensile strength and excessive elongation), poor heat resistance ( _{low T d5%} ), high thermal expansion coefficient, and easy deformation or warpage due to heat. 3. Although Comparative Example 1-15 and Comparative Example 1-16 contain appropriate amounts of (i), (ii), (iii), they are randomly distributed and have no difference between soft and hard segments, and glass transition temperature The temperature is higher than about 350 ^o C, and the bending resistance is not good.

10: substrate 20: Copper circuit 30: Cover film

FIG. 1 is a schematic diagram of a copper foil substrate coated with a polyimide film. From bottom to top, the substrate 10, the copper circuit 20, and the cover film 30 are shown in sequence. The dashed line is the part that is easy to break when bent.

10: substrate

20: Copper circuit

30: Cover film

Claims (24)

A polyimide precursor composition, which comprises the amide ester oligomer of formula (1):

(1) where X has formula (1-a)

The structure of Y has formula (1-b)

In the structure, m ₁ is an integer from 0 to 100; m ₂ is an integer from 1 to 100; m ₃ is an integer from 1 to 100; R _{x is} each independently H, C ₁ -C ₁₄ alkyl, or vinyl-containing Saturated group; R each independently is a C ₁ -C ₁₄ alkyl group, C ₆ -C ₁₄ aryl or aralkyl group, or an ethylenically unsaturated group-containing group; G each independently is a tetravalent organic group ; P _{1 is} each independently a divalent organic group, which includes a divalent siloxane organic group selected from (i) formula (A), (ii) C ₂ -C ₁₄ alkylene group, (iii) formula (B) The group consisting of the divalent group and its combination:

(A)

(B) where R ₆ 'is each independently H, C ₁ -C ₄ alkyl, or phenyl, k may be the same or different and is an integer greater than 0, r is an integer greater than 0, and f is greater than 0 Integer; P _{2 is} each independently a divalent organic group, and its restriction is that P ₂ is not (i) a divalent siloxane organic group of formula (A), (ii) a C ₂ -C ₁₄ alkylene group or (iii) The divalent group of formula (B); and the total content of (i), (ii), (iii) and their combination is 0.5 moles based on the total moles of _{P 1} and P _{2 groups} Ear% to 20 mol%. The polyimide precursor composition of claim 1, wherein m ₁ is an integer from 0 to 50, m ₂ is an integer from 1 to 50, and m ₃ is an integer from 1 to 50. The polyimide precursor composition of claim 1, wherein the sum of _{m 1} , m ₂ , and m _{3 is 2-100.} According to the polyimide precursor composition of claim 1, wherein the ratio of the sum of _{m 1} and m _{3 to m 2} is between 0.1 and 0.5. The polyimide precursor composition of claim 1, wherein k is an integer between 2 and 5. The polyimide precursor composition of claim 1, wherein r is an integer between 1 and 60. Such as the polyimide precursor composition of claim 1, wherein the total content of (i), (ii), (iii) and their combinations is 1 mole based on the total moles of _{P 1} and P _{2 groups} Ear% to 15 mol%. Such as the polyimide precursor composition of claim 1, wherein the group of formula (A) in (i) is selected from the group consisting of:

,

,

,

, And combinations thereof; wherein r is an integer between 1 and 60. The polyimide precursor composition of claim 8, wherein the group of formula (A) of (i) is

or

. Such as the polyimide precursor composition of claim 1, wherein the group (ii) is selected from the group consisting of:

,

,

,

,

, And combinations thereof. Such as the polyimide precursor composition of claim 1, wherein the group of formula (B) in (iii) is selected from the group consisting of:

,

,

, And combinations thereof. The polyimide precursor composition of claim 1, wherein P ₁ further comprises a divalent aromatic group or a divalent heterocyclic group independently of each other. The polyimide precursor composition of claim 1, wherein P _{2 is} each independently a divalent aromatic group or a divalent heterocyclic group. The polyimide precursor composition of claim 12 or 13, wherein the divalent aromatic group or divalent heterocyclic group is selected from the group consisting of:

And combinations thereof; wherein R _{9 is} each independently H, C ₁ -C ₄ alkyl, C ₁ -C ₄ perfluoroalkyl, C ₁ -C ₄ alkoxy, halogen, -OH, -COOH, -NH ₂ or -SH; a and b are each independently an integer from 0 to 4; and R ₁₀ is a covalent bond or a group selected from the group consisting of: -O-, -S-, -CH ₂ -, -S(O) ₂ -、

,

, -C(CF ₃ ) ₂ -, -C(O)-, -C(CH ₃ ) ₂ -, -CONH-,

,

,

and

; Wherein, c and d are each independently an integer from 0 to 20; R ₉ and a are as described above; and R ₁₂ is -S(O) ₂ -, -C(O)-, covalent bond, C _1- C ₄ alkyl or C ₁ -C ₄ perfluoroalkyl. Such as the polyimide precursor composition of claim 12 or 13, wherein the divalent aromatic group or the divalent heterocyclic group is selected from the group consisting of:

; Wherein, a is each independently an integer from 0 to 4; and Z is each independently H, methyl, trifluoromethyl or halogen. Such as the polyimide precursor composition of claim 1, wherein G is selected from the group consisting of:

; Where X is each independently hydrogen, halogen, C ₁ -C ₄ perfluoroalkyl or C ₁ -C ₄ alkyl, and each occurrence of A and B is independently a covalent bond, unsubstituted or through one or more substituents selected from hydroxy and C ₁ -C ₄ alkyl group substituted with the C ₁ -C ₄ alkylene, perfluoro C ₁ -C ₄ alkylene, C ₁ -C ₄ alkoxy stretched, stretch silicon group , -O-, -S-, -C(O)-, -OC(O)-, -S(O) ₂ -, -C(=O)O-(C ₁ -C ₄ alkylene)- OC(=O)-, -CONH-, benzene, biphenyl or

, Wherein K is -O-, -S(O) ₂ -, C ₁ -C ₄ alkylene or C ₁ -C ₄ perfluoroalkylene, and wherein r is an integer from 1 to 60. Such as the polyimide precursor composition of claim 16, wherein G is selected from the group consisting of:

Where Z is each independently H, methyl, trifluoromethyl or halogen. The polyimide precursor composition of claim 1, which further comprises a diamine compound having the structure of the following formula (2): D-NH-P'-NH-D (2) wherein P'is independently two Valence organic group; D is each independently H, unsubstituted or _{C 1} -C ₈ alkyl _{substituted with one or more groups selected from C 6} -C ₁₄ aryl and nitrogen-containing heterocyclic group, unsubstituted An oxygen-containing heterocyclic group substituted or substituted with one or more groups selected from the group consisting of C ₁ -C ₈ alkyl, C ₁ -C ₈ hydroxyalkyl, pendant oxy and -NO _{2, unsubstituted or substituted with one} Or more nitrogen-containing heterocyclic groups substituted with groups selected from pendant oxy groups, C ₁ -C ₈ alkyl groups and -NO _2,

,or

; R ₁ is H, unsubstituted or substituted by one or more groups selected from C ₁ -C ₈ alkyl and C ₁ -C ₈ haloalkyl, C ₆ -C ₁₄ aryl, nitrogen-containing heterocycle Group, C ₄ -C ₁₀ cycloalkyl group, unsubstituted or one or more selected from C ₆ -C ₁₄ aryl group, nitrogen-containing heterocyclic group, -SR ₄ ,

_{C 1} -C ₈ alkyl or C ₁ -C ₈ alkoxy, C ₁ -C ₈ haloalkyl, C ₁ -C ₈ haloalkoxy, or -NR ₅ R ₆ substituted by the group of -CN ; R ₁₃ is

,

, -OR ₁₅ , or C ₁ -C ₁₀ alkoxy; R ₄ , R ₅ and R ₆ may be the same or different and are each independently H, unsubstituted or through one or more C ₆ -C ₁₄ aryl groups Substituted C ₁ -C ₈ alkyl or C ₁ -C ₈ alkoxy, unsubstituted or C ₆ -C substituted with one or more groups selected from C ₁ -C ₈ alkyl and -NO _{2 14} aryl or C ₆ -C ₁₄ aryloxy or nitrogen-containing heterocyclic group; R ₁₄ is (meth)acryloyloxy; R ₁₅ is C ₄ -C ₁₀ cycloalkyl or oxygen-containing heterocyclic group; and t is an integer from 1 to 20. According to the polyimine precursor composition of claim 1, wherein based on the total weight of the polyimine precursor composition, the content of the amide ester oligomer of the formula (1) is about 5 wt% to about 95wt%. The polyimide precursor composition of claim 1, which further comprises a solvent, wherein the solvent is selected from the group consisting of: dimethyl sulfene, diethyl sulfene, tetrahydrofuran, dioxane, dioxolane, cyclic Propylene glycol methyl ether, tetraethylene glycol dimethyl ether, γ-butyrolactone, xylene, toluene, hexamethyl phthalamide, propylene glycol methyl ether acetate,

,

,

And a group consisting of a mixture thereof; wherein: R ₁ '' is independently H, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl or C ₂ -C ₂₀ alkynyl; R ₇ '' is H Or C ₁ -C ₃ alkyl; R ₂ '' is H, C ₁ -C ₁₅ alkyl or C ₄ -C ₈ cycloalkyl; R ₃ '' and R ₄ '' are each independently C ₁ -C ₁₀ Alkyl group, or R _{3 ”} and R _4” together with the nitrogen atom to which they are connected, form a 5- to 6-membered heterocyclic ring; R _{6 ”} is C ₁ -C ₁₅ alkyl, C ₂ -C ₂₀ alkenyl or C ₄ -C ₈ cycloalkyl. A dry film comprising a supporting substrate and a resin layer on the supporting substrate, wherein the resin layer comprises the composition according to any one of claims 1 to 20, and wherein the solvent content of the resin layer is The total weight of the resin layer is at least 5 wt%. A polyimide film, which is prepared from the precursor composition according to any one of claims 1 to 20. A use of the polyimide precursor composition according to any one of claims 1 to 20 or the dry film according to claim 21, which is used as a cover film or a dielectric layer of a printed circuit board. A use of the polyimide precursor composition according to any one of claims 1 to 20 or the dry film according to claim 21, which is used as a dielectric layer of a semiconductor.

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