TWI797993B - Photoresist film and application thereof - Google Patents

Abstract

A photoresist film and application thereof are provided. The photoresist film has a shear loss modulus G'' at 30 ^oC and a shear storage modulus G' at 30 ^oC, wherein the ratio of G'' to G' ranges from 0.50 to 10.40.

Description

Photoresist film and its application

The invention relates to a photoresist film, in particular to a high-thickness photoresist film and the application of the photoresist film.

Photoresist films are generally composed of resins, photosensitive materials and additives. According to the changes after exposure and development, they are divided into positive photoresist films and negative photoresist films. After the positive photoresist film is exposed, the part exposed to light will dissolve during development, and the pattern of the unexposed part will remain after development. After the negative photoresist film is exposed, the part that is not exposed to light will dissolve during development, and the pattern of the exposed part will be left after development.

In the printed circuit board (PCB) industry, photoresist films must be used for etching to form circuit patterns. As electronic components become more and more complex and bulky, the demand for thick photoresist films with high aspect ratios in the printed circuit board industry is gradually increasing. However, problems such as poor adhesion between the existing photoresist film and the substrate, or wrinkles in the appearance, or glue flow during lamination, resulting in uneven thickness of the photoresist film and affecting the etching accuracy, are still urgently needed. improved.

In view of the above-mentioned technical problems, the present invention aims to provide a high-thickness photoresist film with good operability, adhesion, and appearance.

Therefore, an object of the present invention is to provide a photoresist film which has a shear loss modulus (shear loss modulus) G'' value at 30 ^o C and a shear storage modulus (shear loss modulus) at 30 ^o C storage modulus) G' value, wherein the ratio of the G'' value to the G' value (G"/G') is 0.50 to 10.40. In some embodiments of the present invention, the G'' value is relative to The ratio of the G' values is 0.50 to 10.36.

In some embodiments of the present invention, the shear storage modulus G' value at 30 ^o C is 0.001 kPa to 4300 kPa, and the shear loss modulus G'' value at 30 ^o C is 0.08 kPa to 1900 kPa.

In some implementations of the present invention, the shear loss modulus G'' value at 30 ^o C and the shear storage modulus G' value at 30 ^o C are measured by a rheometer under the following operating conditions Obtained: the fixture is 25 mm parallel plate type ETC aluminum, the mode is shear mode, the soak time is 0 seconds, the initial temperature is 30 ^o C, the heating rate is 3 ^o C/min, and the final temperature is 150 ^o C, the resting time after heating is 0 seconds, the pressure is 1000 Pa, single-point measurement, and the frequency is 1 Hz.

In some embodiments of the present invention, the thickness of the photoresist film is 60 microns to 600 microns, for example, 65 microns to 400 microns.

In some embodiments of the present invention, the photoresist film is a negative photoresist film.

In some embodiments of the present invention, the negative photoresist film includes: a (meth)acrylic polymer having a carboxyl group and a photopolymerization initiator.

Another object of the present invention is to provide a composite film, which comprises the above-mentioned photoresist film, and a protective film formed on at least one surface of the photoresist film.

In some embodiments of the present invention, the protective film is selected from the group consisting of polyethylene terephthalate film, polyolefin film and the aforementioned composites.

In order to make the above-mentioned purpose, technical features and advantages of the present invention more comprehensible, the following is a detailed description of some specific implementations.

The following will specifically describe some specific implementation aspects according to the present invention; however, the present invention can be practiced in many different forms, and the protection scope of the present invention should not be construed as being limited to what is stated in the description.

Unless otherwise stated herein, the terms "a", "the" and similar terms used in this specification (especially in the appended claims) should be understood to include both singular and plural forms.

Unless otherwise stated in the text, "(meth)acrylic acid" used in this specification is intended to cover both "acrylic acid" and "methacrylic acid", for example, "(meth)acrylic polymer having carboxyl groups" Both acrylic polymers having carboxyl groups and methacrylic polymers having carboxyl groups are intended to be covered. The term "(meth)acrylate" used in this specification is intended to cover acrylate and methacrylate, for example, "methyl (meth)acrylate" is intended to cover methyl acrylate and methyl methacrylate.

Compared with the prior art, the effect of the present invention lies in that by controlling the rheological properties of the photoresist film, it can provide a thick photoresist film with good adhesion, good appearance and operability. The following provides a detailed description of the photoresist film of the present invention and its application.

1. Photoresist film

The photoresist film of the present invention has specific rheological properties. In the present invention, the photoresist film can be prepared by using appropriate polymeric compounds. The rheological properties and exemplary preparation methods of the photoresist film are described below.

1.1. Rheological Properties of Photoresist Films

The photoresist film of the present invention has a shear loss modulus G'' value at 30 ^o C and a shear storage modulus G' value at 30 ^o C, wherein the G'' value is relative to the G' value The ratio of 0.50 to 10.40, such as 0.50, 0.55, 0.60, 0.65, 0.70, 0.75, 0.80, 0.85, 0.90, 0.95, 1.00, 1.05, 1.10, 1.15, 1.20, 1.25, 1.30, 1.35, 1.40, 1.45, 1.50, 1.55, 1.60, 1.65, 1.70, 1.75, 1.80, 1.85, 1.90, 1.95, 2.00, 2.05, 2.10, 2.15, 2.20, 2.25, 2.30, 2.35, 2.40, 2.45, 2.50, 2.55, 2.60, 2.65, 2.70, 2.75, 2.80, 2.85, 2.90, 2.95, 3.00, 3.05, 3.10, 3.15, 3.20, 3.25, 3.30, 3.35, 3.40, 3.45, 3.50, 3.55, 3.60, 3.65, 3.70, 3.75, 3.80, 3.85, 3.90, 3.95, 4.00, 4.05,4.10,4.15,4.20,4.25,4.30,4.35,4.40,4.45,4.50,4.55,4.60,4.65,4.70,4.75,4.80,4.85,4.90,4.95,5.00,5.05,5.10,5.15,5.20,5.25, 5.30, 5.35, 5.40, 5.45, 5.50, 5.55, 5.60, 5.65, 5.70, 5.75, 5.80, 5.85, 5.90, 5.95, 6.00, 6.05, 6.10, 6.15, 6.20, 6.25, 6.30, 6.35, 6.40, 6.45, 6.50, 6.55,6.60,6.65,6.70,6.75,6.80,6.85,6.90,6.95,7.00,7.05,7.10,7.15,7.20,7.25,7.30,7.35,7.40,7.45,7.50,7.55,7.60,7.65,7.70,7.75, 7.80, 7.85, 7.90, 7.95, 8.00, 8.05, 8.10, 8.15, 8.20, 8.25, 8.30, 8.35, 8.40, 8.45, 8.50, 8.55, 8.60, 8.65, 8.70, 8.75, 8.80, 8.85, 8.90, 8.95, 9.00, 9.05, 9.10, 9.15, 9.20, 9.25, 9.30, 9.35, 9.40, 9.45, 9.50, 9.55, 9.60, 9.65, 9.70, 9.75, 9.80, 9.85, 9.90, 9.95, 10.00, 10.05, 10.10, 10.15, 10.25, 10.30, 10.35 or 10.40, or within the range formed by any two values above. In some embodiments of the present invention, the ratio of the G'' value to the G' value (G"/G') is 0.50 to 10.36. If the ratio of the G'' value to the G' value is less than If the above range, the adhesion of the photoresist film to the substrate is not good; on the contrary, if the ratio of the G'' value to the G' value is greater than the above range, wrinkles will appear on the surface of the photoresist film, and even it will be damaged during operation. The glue flow problem occurs, which in turn causes uneven thickness of the photoresist film and affects the etching accuracy.

Under the conditions of the above-mentioned ratio of the G'' value to the G' value, the value of the shear storage modulus G' of the photoresist film at 30 ^o C is not particularly limited, and can be adjusted as needed. Generally speaking, the shear storage modulus G' value of the photoresist film at 30 ^o C can be 0.001 kPa to 4300 kPa, such as 0.001 kPa, 0.005 kPa, 0.01 kPa, 0.05 kPa, 0.1 kPa, 0.5 kPa, 1 kPa , 5 kPa, 10 kPa, 20 kPa, 30 kPa, 40 kPa, 50 kPa, 60 kPa, 70 kPa, 80 kPa, 90 kPa, 100 kPa, 150 kPa, 200 kPa, 250 kPa, 300 kPa, 350 kPa, 400 kPa, 450 kPa, 500 kPa, 550 kPa, 600 kPa, 650 kPa, 700 kPa, 750 kPa, 800 kPa, 850 kPa, 900 kPa, 950 kPa, 1000 kPa, 1050 kPa, 1100 kPa, 1150 kPa, 1200 kPa, 1250 kPa, 1300 kPa, 1350 kPa, 1400 kPa, 1450 kPa, 1500 kPa, 1550 kPa, 1600 kPa, 1650 kPa, 1700 kPa, 1750 kPa, 1800 kPa, 1850 kPa, 1900 kPa, 1950 kPa, 2000 kPa, 2050 kPa , 2100 kPa, 2150 kPa, 2200 kPa, 2250 kPa, 2300 kPa, 2350 kPa, 2400 kPa, 2450 kPa, 2500 kPa, 2550 kPa, 2600 kPa, 2650 kPa, 2700 kPa, 2750 kPa, 2800 kPa, 2850 kPa, 2900 kPa, 3000 kPa, 3050 kPa, 3100 kPa, 3150 kPa, 3200 kPa, 3250 kPa, 3300 kPa, 3350 kPa, 3400 kPa, 3450 kPa, 3500 kPa, 3550 kPa, 3600 kPa, 3650 kPa, 3700 kPa, 3750 kPa, 3800 kPa, 3850 kPa, 3900 kPa, 3950 kPa, 4000 kPa, 4050 kPa, 4100 kPa, 4150 kPa, 4200 kPa, 4250 kPa, or 4300 kPa, or the range formed by any two values above. If the G' value is less than the lower limit of the above range, the photoresist film will easily cause uneven thickness after being affected by external force; on the contrary, if the G' value is greater than the upper limit of the above range, the photoresist film will easily cause brittle cracks after being affected by external force . In some embodiments of the present invention, the shear storage modulus G' of the photoresist film at 30 ^o C is 10 kPa to 2100 kPa.

Under the conditions of the above ratio of the G'' value to the G' value, the value of the shear loss modulus G'' of the photoresist film at 30 ^o C is not particularly limited, and can be adjusted as needed. Generally speaking, the shear loss modulus G'' of the photoresist film at 30 ^o C can be from 0.08 kPa to 1900 kPa, such as 0.08 kPa, 0.1 kPa, 0.5 kPa, 1 kPa, 5 kPa, 10 kPa, 20 kPa, 30 kPa, 40 kPa, 50 kPa, 60 kPa, 70 kPa, 80 kPa, 90 kPa, 100 kPa, 150 kPa, 200 kPa, 250 kPa, 300 kPa, 350 kPa, 400 kPa, 450 kPa, 500 kPa, 550 kPa, 600 kPa, 650 kPa, 700 kPa, 750 kPa, 800 kPa, 850 kPa, 900 kPa, 950 kPa, 1000 kPa, 1050 kPa, 1100 kPa, 1150 kPa, 1200 kPa, 1250 kPa, 1300 kPa, 1350 kPa . If the value of G'' is less than the lower limit of the above range, it will be difficult to form a film; otherwise, if the value of G'' is greater than the upper limit of the above range, the thickness of the photoresist film will tend to be uneven. In some embodiments of the present invention, the shear loss modulus G'' at 30 ^o C is 140 kPa to 1860 kPa.

The shear loss modulus G'' value of the photoresist film of the present invention at 30 ^o C and the shear storage modulus G' value at 30 ^o C are measured by a rheometer under the following operating conditions: the clamp is 25 Millimeter parallel plate ETC aluminum, the mode is shear mode, the resting time is 0 seconds, the initial temperature is 30 ^o C, the heating rate is 3 ^o C/min, the final temperature is 150 ^o C, and the resting time after heating is 0 seconds, a pressure of 1000 Pa, a single point measurement, and a frequency of 1 Hz. The detailed measurement method is as described in the paragraph of the embodiment.

The ratio (G"/G') of the shear loss modulus G'' value at 30 ^o C and the shear storage modulus G' value at 30 ^o C of the photoresist film of the present invention can be transmitted through the control photoresist film Adjust the proportion of the residual solvent, or by controlling the composition of the photoresist film, such as by controlling the type of resin used to prepare the photoresist film, or the ratio of resin and crosslinking agent used to prepare the photoresist film. Generally In general, the lower the residual solvent ratio of the photoresist film, the smaller the G"/G' value, and the higher the glass transition temperature (Tg) of the resin or the higher the ratio of resin to crosslinking agent (that is, the higher the proportion of resin Higher), the smaller the value of G"/G'.

The photoresist film of the present invention not only has good operability, adhesion, and appearance, but also has the advantage of being able to be formed into a photoresist film with a high thickness. Generally speaking, the thickness of the photoresist film of the present invention can be from 60 microns to 600 microns, more specifically from 65 microns to 400 microns, such as 60 microns, 65 microns, 70 microns, 75 microns, 80 microns, 85 microns, 90 microns Micron, 95 micron, 100 micron, 105 micron, 110 micron, 115 micron, 120 micron, 125 micron, 130 micron, 135 micron, 140 micron, 145 micron, 150 micron, 155 micron, 160 micron, 165 micron, 170 micron, 175 microns, 180 microns, 185 microns, 190 microns, 195 microns, 200 microns, 205 microns, 210 microns, 215 microns, 220 microns, 225 microns, 230 microns, 235 microns, 240 microns, 245 microns, 250 microns, 255 microns , 260 microns, 265 microns, 270 microns, 275 microns, 280 microns, 285 microns, 290 microns, 295 microns, 300 microns, 305 microns, 310 microns, 315 microns, 320 microns, 325 microns, 330 microns, 335 microns, 340 microns Micron, 345 micron, 350 micron, 355 micron, 360 micron, 365 micron, 370 micron, 375 micron, 380 micron, 385 micron, 390 micron, 395 micron, 400 micron, 405 micron, 410 micron, 415 micron, 420 micron, 425 microns, 430 microns, 435 microns, 440 microns, 445 microns, 450 microns, 455 microns, 460 microns, 465 microns, 470 microns, 475 microns, 480 microns, 485 microns, 490 microns, 495 microns, 500 microns, 505 microns , 510 microns, 515 microns, 520 microns, 525 microns, 530 microns, 535 microns, 540 microns, 545 microns, 550 microns, 555 microns, 560 microns, 565 microns, 570 microns, 575 microns, 580 microns, 585 microns, 590 Micron, 595 micron, or 600 micron, or the range formed by any two values above. In some embodiments of the present invention, the thickness of the photoresist film is 65 microns to 350 microns. Since the higher the thickness of the photoresist, the higher the plateable thickness of the metal conductive layer, the photoresist film of the present invention is particularly suitable for 2.5D and 3D integrated circuit packaging, and can be used as a patterning application before electroplating of the conductive layer, which can meet more requirements. Wide range of applications.

The photoresist film of the present invention can be a positive photoresist film or a negative photoresist film. In some embodiments of the present invention, the photoresist film of the present invention is a negative photoresist film, that is, after the photoresist film is exposed, the part that is not exposed to light will dissolve during development, and the exposed part will remain after development picture of.

1.2. Composition of photoresist film

Under the condition that the ratio of the shear loss modulus G'' value at 30 ^o C and the shear storage modulus G' value at 30 ^o C is 0.50 to 10.40, the composition of the photoresist film of the present invention can be adjusted as needed . In some embodiments of the present invention, the photoresist film is a negative photoresist film, which includes a (meth)acrylic polymer having a carboxyl group and a photopolymerization initiator, or is substantially composed of a (meth)acrylic polymer having a carboxyl group. base) acrylic polymer and a photopolymerization initiator, or a (meth)acrylic polymer having a carboxyl group and a photopolymerization initiator.

In this article, (meth)acrylic polymers having carboxyl groups are polymers or copolymers formed from (meth)acrylic compounds, or polymers formed from (meth)acrylic compounds and other polymerizable compounds. copolymer. The (meth)acrylic compound refers to a (meth)acrylic compound containing a vinyl group (containing unsaturated double bonds) and a carboxyl group in the molecule, examples of which include but not limited to acrylic acid and methacrylic acid, and each (meth)acrylic acid ) acrylic compounds can be used alone or in combination. The other polymeric compounds can be any unsaturated double bond-containing compounds other than (meth)acrylic compounds, such as vinyl-containing compounds, examples of which include but are not limited to (meth)acrylate compounds and acryl amine. Examples of the (meth)acrylate compounds include, but are not limited to, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, methyl acrylate, Butyl acrylate, 2-ethylhexyl methacrylate, isobutyl acrylate, hydroxypropyl acrylate, 2-hydroxyethyl acrylate, isotridecyl acrylate, o-phenylphenoxyethyl acrylate ester, lauryl acrylate, cyclic trimethylopropane formal acrylate, isodecyl acrylate, octyl acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate , 2-(2-ethoxyethoxy) ethyl acrylate, and 2-phenoxy ethyl acrylate. The above-mentioned polymerizable compounds can be used alone or in any combination.

In a preferred embodiment of the present invention, the (meth)acrylic polymer having a carboxyl group is a copolymer formed from a (meth)acrylic compound and a (meth)acrylic ester compound, wherein (meth) ) the acrylic compound may be acrylic acid, methacrylic acid or combinations thereof, and the (meth)acrylates may be selected from methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, and combinations thereof, and ( The weight ratio of meth)acrylic compound to (meth)acrylic ester can be 0.05 to 0.4, such as 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35 or 0.4, or between any two values above range.

Under the conditions of the ratio of the G'' value to the G' value of the photoresist film of the present invention, the molecular weight of the (meth)acrylic polymer with carboxyl groups contained in the photoresist film is not particularly limited. 30,000 to 200,000, such as 30,000, 35,000, 40,000, 45,000, 50,000, 55,000, 60,000, 65,000, 70,000, 75,000, 80,000, 85,000, 90,000, 95,000, 101,100,000, 10 ,000, 120,000, 125,000, 130,000 . .

In the photoresist film of the present invention, the type of photopolymerization initiator is not particularly limited, and various photopolymerization initiators known in the technical field of the present invention can be used. Examples of the known photopolymerization initiators include but not limited to biimidazole-based compounds and Michler's ketone-based compounds. The content of the photopolymerization initiator in the photoresist film is not particularly limited, as long as it can provide the desired effect of promoting the polymerization reaction. Generally speaking, based on 100 parts by weight of (meth)acrylic polymers with carboxyl groups, the content of the photopolymerization initiator can be 0.5 parts by weight to 15 parts by weight, such as 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15, or within the range formed by any two of the above values.

In a preferred embodiment of the present invention, the photoresist film is a negative photoresist film, which includes the above-mentioned (meth)acrylic polymer with carboxyl groups and a photopolymerization initiator, and further includes a crosslinking agent. The crosslinking agent can be various polyfunctional unsaturated monomers known in the technical field of the present invention, such as polyfunctional acrylate-based unsaturated monomers, examples of which include but are not limited to ethoxylated trimethylolpropane triacrylic acid ester, tripropylene glycol diacrylate, 1,6-hexanediol diacrylate, ethoxylated bisphenol A diacrylate, polypropylene glycol diacrylate, dipentaerythritol hexaacrylate. Under the conditions of the ratio of the G'' value to the G' value of the photoresist film of the present invention, the content of the crosslinking agent in the photoresist film is not particularly limited, as long as the desired crosslinking effect can be provided. Can. Generally speaking, based on 100 parts by weight of (meth)acrylic polymers with carboxyl groups, the content of crosslinking agent can be 10 parts by weight to 100 parts by weight, such as 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95 or 100, or the range formed by any two values above.

In yet another preferred embodiment of the present invention, the photoresist film is a negative photoresist film, which includes the above-mentioned (meth)acrylic polymer with carboxyl group and photopolymerization initiator, and further A solvent is included, and the aforementioned crosslinking agent may be further included if necessary. The solvent can be any inert solvent that can dissolve or disperse the components of the photoresist film, but does not react with these components. Examples of the inert solvent include but are not limited to tetrahydrofuran, acetone, methyl ethyl ketone, methyl acetate, ethyl acetate ester, propylene glycol monomethyl ether, methanol, ethanol, propylene glycol methyl ether acetate, and gamma-butyrolactone. The above-mentioned solvents may be used alone or in any combination.

In addition to the above optional and necessary components, the photoresist film of the present invention may optionally contain various additives known in the technical field of the present invention. Examples of such conventional additives include, but are not limited to, dyes, pigments, free radical inhibitors, and surfactants. Each of these additives may be used alone or in any combination.

1.3. Preparation of photoresist film

The preparation method of the photoresist film of the present invention is not particularly limited, and those with ordinary knowledge in the technical field of the present invention can prepare the photoresist film based on the disclosure of this specification. Taking the preparation of the negative photoresist film mentioned above as an example, the various components of the photoresist film, including (meth)acrylic polymers with carboxyl groups, photopolymerization initiators and other crosslinking agents as needed, can be passed through and additives, uniformly mixed with a stirrer and dissolved or dispersed in a solvent to form a resin composition, and then the obtained resin composition is coated on a substrate and dried to obtain a photoresist film, The preparation of (meth)acrylic polymers having carboxyl groups can be carried out by addition reaction of various polymerizable compounds, such as (meth)acrylic compounds and (meth)acrylic ester compounds, in the presence of catalysts. be made of. The detailed preparation method is illustrated in the following examples, and will not be repeated here.

2. Application of photoresist film

Before the photoresist film is used, both surfaces of the photoresist film are generally covered with a protective layer to facilitate the storage of the photoresist film and prevent the photoresist film from sticking to foreign objects or being damaged. Therefore, the present invention further provides a composite film comprising the above-mentioned photoresist film of the present invention and a protective film formed on at least one surface of the photoresist film. In a preferred embodiment of the present invention, the protective film is formed on the two surfaces of the photoresist film, and the materials of the protective films formed on the two surfaces of the photoresist film can be the same or different.

The type of protective film is not particularly limited, and various materials known in the technical field of the present invention can be used. For example, the protective film that can be used in the present invention can be selected from the following group: polyethylene terephthalate film (PET film), polyolefin film and the aforementioned composites. Examples of the polyolefin film include but are not limited to polyethylene film (PE film) and polypropylene film (PP film), such as oriented polypropylene film (oriented polypropylene film), and the composite may be polyethylene terephthalic acid Composite of ethylene glycol film and polyolefin film, or composite of different polyolefin films. In a preferred embodiment of the present invention, the composite film includes a PET film formed on one surface of the photoresist film and a PE film formed on the other surface of the photoresist film.

The preparation method of the composite membrane of the present invention is not particularly limited, and the known methods in the field of the present invention can be used. Those with ordinary knowledge in the technical field of the present invention can prepare the composite membrane based on the disclosure of this case specification. For example, a protective film may be laminated on both surfaces of a photoresist film to provide a laminate, and the laminate may be pressed to obtain a composite film. Alternatively, the resin composition for forming a photoresist film may be first coated on the first protective film and dried to form a photoresist film on the first protective film, and then the photoresist film is not separated from the first protective film. A second protective film is pasted on the surface in contact with the protective film, thereby obtaining a composite film. Alternatively, the resin composition for forming the photoresist film can also be extruded between two protective films with a fixed distance, and then dried to form a photoresist film between the two protective films.

3. Example

3.1. measurement method

[Measurement of shear storage modulus G' value and shear loss modulus G'' value]

Fold the photoresist film several times and exclude air bubbles to a thickness of 1.2 mm to 1.4 mm as a sample, and use a rheometer (model: Discovery HR-2, TA Instruments; Trios software version: 3.1.0.3538) to measure the sample, The operating conditions are as follows: the sample holder is 25 mm parallel plate ETC aluminum, the mode is shear mode, the resting time is 0 seconds, the initial temperature is 30 ^o C, the heating rate (ramp rate) is 3 ^o C/min, The final temperature is 150 ^o C, the soak time after heating is 0 seconds, the pressure is 1000 Pa, single-point measurement, and the frequency is 1 Hz. Record the shear loss modulus G'' value at 30 ^o C and the shear storage modulus G' value at 30 ^o C, and calculate the ratio of G'' value to G' value (G"/G' ).

[Photoresist Wrinkle Test]

The prepared composite film was rolled into a slit roll with a length of 30 meters and a width of 300 mm, and placed at a temperature of 23 ^o C to 27 ^o C for 1 hour. Afterwards, pull out a 5-meter-long composite film from the slitting roll and tear off the PE protective film, then observe the surface of the photoresist film with the naked eye, and record the presence of the photoresist film at a length of 3 meters to 5 meters The number of wrinkles longer than 10 mm and wider than 1 mm.

[Photoresist Film Adhesion 100-Grid Test]

The photoresist film adhesion test is carried out in the following manner according to ASTM D3359. Prepare a copper foil laminated board (available from Changchun Synthetic Resin Factory Co., Ltd., model number CCP-308) with a thickness of 1.6 mm, wherein the thickness of the copper foil is 35 microns. Use #320 non-woven brush wheel and #600 non-woven brush wheel to brush it, and adjust the copper foil surface temperature of the copper foil laminate to 50 ^o C. The PE protective film on the surface of the composite film is torn off, and then the photoresist film and the PET protective film on it are laminated on the surface of the copper foil with the photoresist film facing the copper foil surface of the copper foil laminated board, and then The film was pressed by a film laminator to prepare the samples, wherein the film pressing temperature was 80 ^o C, the film pressing pressure was 3.0 kg/cm2, and the film pressing speed was 2.0 m/min. The PET protective film on the sample is torn off, and the photoresist film on the sample is cut into a square of 10×10 with a total of 100 grids at an interval of 1 mm to 1.2 mm with a blade. Stick the transparent tape (model: 3M Transparent 600) produced by 3M Company on the surface of the photoresist film at the cutting place, then pull up the tape instantly at an angle of 45 degrees to the substrate, calculate and record the peeling rate of the photoresist film The percentage of the number to the total number of grids.

[Glue flow test]

Prepare a copper foil laminate with a thickness of 1.6 mm, wherein the thickness of the copper foil is 35 microns. Use #320 non-woven cloth brush wheel and #600 non-woven cloth brush wheel to brush it, and adjust the copper foil surface temperature of the copper foil laminate to 50 ^o C. The PE protective film on the surface of the prepared composite film is torn off, and the photoresist film and the PET protective film on it are stacked on the surface of the copper foil with the photoresist film facing the copper foil surface of the copper foil laminated board, and then pressed The film is laminated by a film machine, wherein the lamination temperature is 80 ^o C, the lamination pressure is 3.0 kg/cm2, and the lamination speed is 2.0 m/min. Observe with the naked eye whether there is resin flowing out from the edge of the photoresist film during the lamination process, and if so, it is judged to be glue flow.

3.2. Preparation and testing of photoresist film

3.2.1. Synthesis of Acrylic Polymers with Carboxyl Groups

[Synthesis Example 1]

15 g of methacrylic acid, 60 g of methyl methacrylate, and 25 g of butyl acrylate as copolymerizable monomers were mixed with 0.5 g of azobisisoheptanonitrile to prepare a solution a1. Separately, 0.5 g of azobisisoheptanonitrile was dissolved in 20 g of ethyl acetate solvent to prepare a solution b1. Prepare a flask equipped with a stirrer, a reflux cooler, a thermometer, and a dropper, add 80 grams of ethyl acetate solvent in the flask, and heat to 70 ^o C, and then add to the flask at a constant speed for 3 hours Solution a1 was added dropwise, and then the temperature of the solution in the flask was kept at 70 ^o C and stirred for 2 hours. Then, solution b1 was added dropwise to the flask at a constant rate for a total of 0.5 hours, and then the temperature of the solution in the flask was kept at 70 ^° C and stirred for 5 hours. Afterwards, the solution in the flask was heated to 90 ^o C and stirred for 5 hours to allow the reaction to fully proceed. After the reaction was completed, the resultant was cooled to room temperature to obtain an acrylic polymer A having carboxyl groups (hereinafter also referred to as "polymer A") with a weight average molecular weight of 55,000 and a solid content of 50% by weight.

[Synthesis Example 2]

15 g of methacrylic acid, 65 g of methyl methacrylate, and 20 g of butyl acrylate as copolymerizable monomers were mixed with 0.43 g of azobisisoheptanonitrile to prepare a solution a2. Separately, 0.5 g of azobisisoheptanonitrile was dissolved in 20 g of ethyl acetate solvent to prepare solution b2. Prepare a flask equipped with a stirrer, a reflux cooler, a thermometer, and a dropper, add 102.2 grams of ethyl acetate solvent in the flask, and heat to 70 ^o C, then add a total of 3 hours to the flask at a fixed speed Solution a2 was added dropwise, and then the temperature of the solution in the flask was kept at 70 ^o C and stirred for 2 hours. Then, solution b2 was added dropwise to the flask at a constant rate for a total of 0.5 hours, and then the temperature of the solution in the flask was kept at 70 ^° C and stirred for 5 hours. Afterwards, the solution in the flask was heated to 90 ^o C and stirred for 5 hours to allow the reaction to fully proceed. After the reaction was completed, the product was cooled to room temperature to obtain an acrylic polymer B having carboxyl groups (hereinafter also referred to as "polymer B"), with a weight average molecular weight of 65,000 and a solid content of 45% by weight.

[Synthesis Example 3]

Mix 20 grams of methacrylic acid, 40 grams of methyl methacrylate, and 40 grams of 2-Ethylhexyl Acrylate as copolymerized monomers with 0.5 grams of azobisisoheptanonitrile to prepare solution a3 . Separately, 0.5 g of azobisisoheptanonitrile was dissolved in 20 g of ethyl acetate solvent to prepare solution b3. Prepare a flask equipped with a stirrer, a reflux cooler, a thermometer, and a dropper, add 80 grams of ethyl acetate solvent in the flask, and heat to 70 ^o C, and then add to the flask at a constant speed for 3 hours Solution a3 was added dropwise, and then the temperature of the solution in the flask was kept at 70 ^o C and stirred for 2 hours. Then, solution b3 was added dropwise to the flask at a constant rate for a total of 0.5 hours, and then the temperature of the solution in the flask was kept at 70 ^° C and stirred for 5 hours. Afterwards, the temperature of the solution in the flask was heated to 90 ^o C and stirred for 5 hours to allow the reaction to fully proceed. After the reaction was completed, the product was cooled to room temperature to obtain an acrylic polymer C having carboxyl groups (hereinafter also referred to as "polymer C"), with a weight average molecular weight of 55,000 and a solid content of 50% by weight.

3.2.3. Preparation of photoresist film

In the following examples and comparative examples, the raw material information used is shown in Table 1 below.

Table 1: List of raw material information raw material illustrate Polymer A The acrylic polymer A with carboxyl group prepared in Synthesis Example 1 Polymer B The acrylic polymer B with carboxyl group prepared in Synthesis Example 2 Polymer C The acrylic polymer C with carboxyl group prepared in Synthesis Example 3 3EO TMPTA Crosslinker, ethoxylated trimethylolpropane triacrylate, CAS No.: 28961-43-5 BCIM-HABI Photopolymerization initiator, 1,2'-bis(2-chlorophenyl)-tetraphenylbiimidazole, CAS No.: 7189-82-4 EABF Photopolymerization initiator, 4,4'-bis(diethylamino)benzophenone, CAS No.: 90-93-7 CI42040 Dye, Brilliant green (bisulfate), CAS No.: 633-03-4 THF Solvent, THF, CAS No.: 109-99-9

The components were mixed according to the component ratios shown in Tables 2-1 to 2-3, and stirred for 1 hour to mix uniformly, thereby obtaining a resin composition. After that, according to the coating and drying conditions shown in Tables 2-1 to 2-3, the obtained resin composition was coated on a PET film as a protective film with a Kodaira wire bar, and then dried in an oven. resin composition, then cover the PE film as a protective film on the surface of the resin composition after drying, so as to obtain the photoresist film (i.e. the composite film) covered by the protective film of Examples 1 to 9 and Comparative Examples 1 to 5 ).

table 2-1 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Polymer A (parts by weight; solid content 50% by weight) 200 200 200 200 200 200 3EO TMPTA (parts by weight) 45 45 45 45 45 45 BCIM-HABI (parts by weight) 3 3 3 3 3 3 EABF (parts by weight) 3 3 3 3 3 3 CI42040 (parts by weight) 0.01 0.01 0.01 0.01 0.01 0.01 THF (parts by weight) 10 10 10 10 10 10 Coating thickness (micron) 500 500 500 250 155 1000 Drying temperature ( ^oC ) 100 100 95 95 90 85 Drying time (minutes) twenty four twenty two twenty two twenty two twenty two 20 Thickness after drying (microns) 200 200 200 100 65 400

Table 2-2 Example 7 Example 8 Example 9 Polymer B (parts by weight; solid content 45% by weight) 222 Polymer C (parts by weight; solid content 50% by weight) 200 200 3EO TMPTA (parts by weight) 45 45 45 BCIM-HABI (parts by weight) 3 3 3 EABF (parts by weight) 3 3 3 CI42040 (parts by weight) 0.01 0.01 0.01 THF (parts by weight) 10 10 10 Coating thickness (micron) 250 250 250 Drying temperature ( ^oC ) 115 95 60 Drying time (minutes) twenty two 35 40 Thickness after drying (microns) 100 120 120

Table 2-3 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative Example 5 Polymer A (parts by weight) 200 200 Polymer B (parts by weight) 222 222 Polymer C (parts by weight) 200 3EO TMPTA (parts by weight) 45 45 45 45 45 BCIM-HABI (parts by weight) 3 3 3 3 3 EABF (parts by weight) 3 3 3 3 3 CI42040 (parts by weight) 0.01 0.01 0.01 0.01 0.01 THF (parts by weight) 10 10 10 10 10 Coating thickness (micron) 250 250 250 250 240 Drying temperature ( ^oC ) 115 100 50 60 55 Drying time (minutes) twenty two 35 twenty two twenty two 25 Thickness after drying (microns) 100 100 120 120 115

3.2.4. Photoresist film test

The properties of the photoresist films of Examples 1 to 9 and Comparative Examples 1 to 5 were measured according to the measurement methods mentioned above, including shear storage modulus G' value, shear loss modulus G'' value, and adhesion Baker test, wrinkle test, and glue flow test, and record the results in the following tables 3-1 to 3-3.

Table 3-1 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 G'' (kPa) 1858 985 715 1065 902 145 G' (kPa) 2016 744 448 1055 1790 14 G''/G' ratio 0.92 1.32 1.60 1.01 0.50 10.36 Hundred grid test (percentage) <5% <5% <5% <5% <5% <5% number of wrinkles 0 0 0 0 0 0 Whether glue flow no no no no no no

Table 3-2 Example 7 Example 8 Example 9 G'' (kPa) 628 1131 185 G' (kPa) 405 1190 twenty three G''/G' ratio 1.55 0.95 8.04 Hundred grid test (percentage) <5% <5% <5% number of wrinkles 0 0 0 Whether glue flow no no no

Table 3-3 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative Example 5 G'' (kPa) 1103 1823 98 105 125 G' (kPa) 3929 4050 5.6 10 12 G''/G' ratio 0.28 0.45 17.50 10.50 10.42 Hundred grid test (percentage) >65% 35%-65% <5% <5% <5% number of wrinkles 0 0 15 5 3 Whether glue flow no no yes yes no

As shown in Tables 3-1 to 3-3, the photoresist film of the present invention shows a low peeling ratio (<5%) in the 100-grid test, which means that it has good adhesion to the substrate, no wrinkles, and a good appearance. In addition, the photoresist film of the present invention has no glue flow during operation, and the operation performance is good. In contrast, as shown in Comparative Examples 1 and 2, the ratio of the shear loss modulus G'' value at 30 ^o C to the shear storage modulus G' value at 30 ^o C is below 0.50 In some cases, the adhesion of the photoresist film is not good, and it shows a significantly higher peeling ratio in the 100-grid test. In addition, as shown in Comparative Examples 3 to 5, in the case where the ratio of the shear loss modulus G'' value at 30 ^° C to the shear storage modulus G' value at 30 ^° C is higher than 10.40, The photoresist film will have wrinkles and poor appearance, when the ratio of the shear loss modulus G'' at 30 ^o C to the shear storage modulus G' at 30 ^o C is higher than 10.50 (Comparative examples 3 and 4), the photoresist film may even flow during operation, and the operation performance is not good, which is not conducive to practical application.

The above-mentioned embodiments are only illustrative to illustrate the principles and effects of the present invention, and to illustrate the technical features of the present invention, rather than to limit the protection scope of the present invention. Any change or arrangement that can be easily accomplished by those skilled in the art without violating the technical principle of the present invention falls within the scope of the present invention. Therefore, the scope of protection of the rights of the present invention is listed in the appended patent scope.

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Claims (8)

A photoresist film having a shear loss modulus (shear loss modulus) G" value at 30°C and a shear storage modulus (shear storage modulus) G' value at 30°C, wherein the G" value is relatively The ratio (G"/G') of the G' value is 0.50 to 10.40; the loss modulus G" value at 30°C and the shear storage modulus G' value at 30°C are measured by rheometer Measured under the following operating conditions: the fixture is a 25mm parallel plate type ETC aluminum, the mode is shear mode, the soak time is 0 seconds, the initial temperature is 30°C, the heating rate is 3°C/min, and the final temperature The temperature is 150° C., the standing time after heating is 0 seconds, the pressure is 1000 Pa, single-point measurement, and the frequency is 1 Hz; and the photoresist film is a negative photoresist film. The photoresist film according to claim 1, wherein the ratio of the G" value to the G' value is 0.50 to 10.36. The photoresist film according to Claim 1, wherein the shear storage modulus G' value at 30°C is 0.001kPa to 4300kPa, and the shear loss modulus G" value at 30°C is 0.08kPa to 1900kPa . The photoresist film according to any one of claims 1 to 3 has a thickness of 60 microns to 600 microns. The photoresist film as described in Claim 4 has a thickness of 65 microns to 400 microns. The photoresist film according to claim 1, comprising a (meth)acrylic polymer having a carboxyl group and a photopolymerization initiator. A composite film comprising: the photoresist film according to any one of claims 1 to 6; and a protective film formed on at least one surface of the photoresist film. The composite film as described in claim 7, wherein the protective film is selected from the following group: polyethylene terephthalate film, polyolefin film and the aforementioned composites.