JPS587628A - Photosensitive laminated structure - Google Patents

Abstract

PURPOSE:To obtain the titled structure having a superior antistatic property and superior properties of isolating oxygen and transmitting ultraviolet rays by laminating a photoresist layer on a specified stretched polyvinyl alcohol film. CONSTITUTION:An unstretched polyvinyl alcohol film having >=500 polymn. degree and >=98mol% saponification degree is uni- or biaxially stretched by >=1.5 times and heat-treated at >=150 deg.C to obtain a stretched polyvinyl alcohol film A having <=5cc/m<2>/24hr oxygen permeability at 20 deg.C and 65% RH and >=35% crystallinity. A photoresist layer B is laminated on the film A, or a film C such as a polyethylene film is further laminated to obtain a photosensitive laminated structure. After exfoliating the film C, the layer B is superposed on a metallic surface in close contact with each other, and it is exposed through the film A. The film A is then exfoliated, and the unexposed part of the layer B is dissolved and removed to develop the layer B.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photosensitive laminated structure having a structure in which at least four pieces of WJK film are laminated with a photoresist layer.

A photosensitive laminated structure in which 7 photoresist layers are formed on a transparent support such as polyethylene terephthalate film or polyolein film, and a protective film such as polyethylene film is further laminated on top of No. 6. The product is known, and the image 0@ku shows that after peeling and removing the protective film from this laminated structure, the seven odoresist layers are piled up and pressed together so that they are in contact with a metal surface such as a steel plate, and the dew point is applied.
The support is peeled off and then developed with a solvent type developer, an alkaline type developer, etc. for several seconds.

However, films such as polyethylene terephthalate film, which are used as optically transparent supports,
(1) Problems such as the film clinging to the hand due to charging during the peeling process after exposure, (1) - elemental blocking properties are insufficient, and ultraviolet light transmission is not always sufficient. (4) There is a tendency for there to be disadvantages in terms of exposure time and sensitivity;
The adhesive strength of the photoresist layer and the adhesive strength of the photoresist layer/support body are made to be significantly different, so that the adhesive strength of the former is smaller than that of the latter, and the adhesive strength of the latter is also the same as that of the photoresist layer. The strength must be kept to a level that does not cause damage, but since the protective film and the support are made of resins of the same type of wood, it is difficult to control the difference in the force between each layer. (1) Depending on the material of the support, heat resistance may be insufficient when hot and press-bonded to a metal surface.

The present invention solves the problems of the conventional method as described above.

The photosensitive laminated structure of the present invention has a layer structure consisting of film/photoresist layer B/y film C,
In the case of (4), the film is left as it is, and in the case of (b), the film is peeled off, then polymerized and adhered so that the metal @Kl comes into contact with the film. A: 1) Stretching ratio is at least 1.5 times or more in 4-axis, I) 2
At 0°C and 65% IIIK, the release rate of Shunmoto is 5 QC/v
It is characterized by using a stretched polyvinyl alcohol film that satisfies all of the following conditions: d/24h, r or less; (2) crystallinity of 35g6 or more;

The present invention provides the following excellent effects.

+11 It has excellent antistatic properties, so there are no problems such as the film clinging to your hands during peeling after exposure.7 (Grown) It is easy to handle because it does not attract dust.

It has extremely excellent light-blocking properties S and excellent ultraviolet transmittance, so exposure time can be shortened and sensitivity and resolution are also good.

G41 In the A/B/C layer structure, there is a clear difference in the interlayer adhesion of B/C and A/L, and the adhesion can be further improved by adjusting the crystallinity of Mu. Since #lc can be set arbitrarily, IK peeling errors will not occur when C is peeled off, and the #lc will not be damaged when peeling off after exposure.

11) Since the heat resistance is good, heat and pressure bonding to the gold M surface (KIIL) does not cause any trouble.

The above-mentioned remarkable effects of the present invention are the above-mentioned special i! O
This can only be achieved by using a polyvinyl alcohol stretched film that satisfies the conditions, and even if a normal unstretched polyvinyl alcohol film is used instead of the polyvinyl alcohol stretched film, such excellent effects cannot be achieved. When using a normal unstretched polyvinyl alcohol film, the physical properties change greatly depending on the environmental conditions, and the photoresist pattern on the film cannot be smoothly applied. There are problems such as not necessarily having sufficient properties, adhesion with the k17 photoresist layer tending to be too strong, and peeling of the film after exposure may not be smooth.

The present invention (in particular, the polyvinyl alcohol film constituting the film is required to satisfy all of the conditions (El) to (■) as mentioned above).

I) The stretching ratio is 1.5 times or more in at least one direction.

When the stretching ratio is 1.5 times, for the purpose of the present invention, there is no difference between the unstretched film and the wooden hook KFi, and the desired effect Kti is not sufficiently exerted.

Note that the stretching may be either uniaxial stretching or biaxial stretching, and the preferable magnification is 2 times or more in the case of one-wheel stretching, and 2.5 times or more in area magnification in the case of two-wheel stretching. Particularly preferred is the case of two-wheel stretching with an area magnification of 4 times or more.

I) Oxygen permeability at 20°C and 65% RHfC is 5ce
/d/24k r or less, preferably 2cc/m/24
Must be less than or equal to hr.

If the oxygen permeability exceeds 5 cc/m'/24 krt-, the storage stability of the laminated film will be poor, resulting in a disadvantage in terms of sensitivity.

i) Crystallinity is 55% or more, preferably 40% or more.

If the crystallinity is less than 35%, the physical properties change greatly depending on the environmental conditions, making it difficult to smoothly produce a laminated film, and the adhesive force with the photoresist layer B will be excessive, causing damage to the photoresist layer when it is peeled off after exposure. There is a risk.

There is no particular limitation on the welfare, and it is usually selected from the range of about 7 to 50 voices, but within this range, #i is less than 50 voices, preferably i
It is desirable to set the pitch to be less than 20 tones, more preferably to 17 tones, from the viewpoints of resolution change, prevention of noise and blurring, and shortening of the opening time when irradiated with active light.

In order to obtain a stretched polyvinyl alcohol film that satisfies the above conditions, it is desirable to pay attention to the following points.

It is preferable to use one with a high degree of F (for example, 98% or higher) in terms of improving the strength of the stretched film and improving the e* barrier properties.

・For polyvinyl alcohol stretched films, it is better to use less plasticizer content, or if possible, no plasticizer at all, to improve the dye barrier properties and to reduce the amount of components in the photoresist layer to the film in photosensitive laminated structures. Preferable in terms of prevention of migration and improvement of crystallinity.

A higher O stretching ratio is preferable from the viewpoints of improving the strength of the stretched film, making it thinner, improving oxygen barrier properties, and improving the adhesion strength between layers in the photosensitive stack structure and crystallinity.

- After stretching, it is preferable to heat the film to 150° C. or higher in order to improve the dimensional stability, crystallinity, and oxygen barrier properties of the stretched film.

・The mechanical properties of the stretched film include a tensile strength of 2000'
It is preferable that the length is 1 m or more and the initial elastic modulus is 2.0XIO"1 or more.

Next, as the uninvented photoresist layer B, a layer of a known alkali development type, solvent development type, or dry development type photosensitive resin composition can be used.

As the film C in the present invention, the photoresist layer 1
It plays a role as a storage layer or support layer for the film, and examples include polyethylene film, polypropylene film, paper laminated with polyethylene or polypropylene, polyester film, cellulose film, and nylon film. It is required that film C, which is a stretched film, does not strongly adhere to photoresist layer B.

The layer structure a of the laminated structure of the present invention is basically a single-layer structure aK) of film A/photoresist layer B, but usually from the viewpoint of storage, transportation, handling, etc. ... Layer structure e, (b) It is often made into a five-layer structure.

In the layer structure (a), a solvent solution of the photosensitive resin composition may be placed on the film A by any method such as casting, spraying, roll coating, or extrusion coating, and then dried.

In the layer structure vL (b), a method is adopted in which 7 photoresist layers B are formed on film A, and then film Cf is laminated thereon, and 7 photoresist layers B are first formed on film C, A method may also be adopted in which the film A is then laminated from the above steps.

The thus obtained laminated structure having a layer structure of A/B or tiA/B/C is stored by being deposited or rolled,
It will be shipped and put into practical use.

The method of using the uninvented photosensitive laminate structure is not particularly different from conventional methods. To describe a typical case, 1@structure (a) K remains as it is, but film C is peeled off first in layer structure tL@KTo. Next, a laminate made of paper A/II is stacked so that the metal *KBili such as a copper-clad laminate is in contact with the metal surface, and bonded under pressure. At this time, pressure bonding is usually performed using a heated roll.

2. Place the original image on the film A side and expose it to active light.

1. Peel off the exposure machine film A. Dissolve and remove the unexposed portions of the photoresist jB with a 3° C.m developing solution and develop.

1. Copper plating, solder plating, resist peeling, copper etching, etc. are performed in accordance with conventional methods.

The invention will now be further explained by way of example. The crystallinity and oxygen permeability were measured as follows.

Crystallinity The density at 25°C was measured using a density tube using ditetrachloride and xylene, and the crystallinity of the paper was calculated from the density.

Oxygen permeability: 20℃,! 5961H for 100 hours and the oxygen permeability of 65% at 20°C for nine samples.
Measured with ON OX-TRAM 100.

Example I A: Stretching ratio: 7.5 times (length: 5 times, width: 2.5 times), thickness: 1
5 voices, oxygen permeability 0-6'! /m/24h r (2
0°C, 65% RH), polyvinyl alcohol biaxially stretched film with crystallinity of 46g6 (plasticizer usage amount 0, after stretching 2
Treatment at 10°C for 20 seconds, degree of polymerization of polyvinyl alcohol 1700, degree of saponification 99 mol%, tensile degree 50
B: Alkali-soluble acrylic copolymer photoresist C: Methyl ethyl ketone solution of B was applied onto polyethylene terephthalate film C with a thickness of 50 μm using a roll coater. Please be polite. Thickness of l after tt image #i25
μ and nine. Next, layer A was layered on top of Kl and pressed to form a 6-layer structure of #) A/B/C, which was then rolled.

After peeling C from the above laminated structure, K on the copper-clad laminate
Layer A and B so that the B sides are in contact and bond by heating and pressurizing at a temperature of 100°C.

Next, an original sheet was placed on the A side, exposed to light using an exposure machine (exposure dose: 90 millijoules), and then the film was peeled off. Then, with a developer consisting of a 296 aqueous solution of sodium acid,
Developing was performed for a minute.

The results are shown in the first barley.

Comparative Example 1 B of Example 1 was coated on a polyethylene terephthalate film having a thickness of 50 μm, and then a polyethylene film was overlaid and pressure-bonded to form a five-layer structure, which was then rolled.

The polyethylene film was peeled off from the above laminated structure, and the copper-plated 9 laminate was stacked so that the KB sides were in contact with each other, and the temperature was 1.
Adhesion was achieved by heating and pressing at 00°C.

Then, from above the polyethylene terephthalate film,
1 [Place the Ili sheet and expose to light using an exposure machine with an exposure dose of 90 mD], then peel off the polyethylene terephthalate film. Next, the film was developed for 5 minutes with a developer consisting of 2 g of sodium carbonate in water.9.

The results are shown in conjunction with No. 111.

Control Examples 2 to 5 Experiments were conducted in the same manner as in Example 1 except for the use of the following films in place of polyvinyl alcohol biaxially stretched film A.

The results are also shown in Table 1.

Control example 2 Polyvinyl alcohol rice stretched film with a thickness of 25 mm (polyvinyl alcohol 01 degree 1800, degree of saponification 99 mol%, plasticizer content 11%) Control example 5 Stretching ratio - times (2 times vertical, 2 times horizontal), thickness 18P1 Oxygen Passage 4o:/d/24hr (20℃, 65*RH)
, 111+1+ polyvinyl alcohol two-wheel stretched film with a degree of 52% (plasticizer content O11, weight of polyvinyl alcohol 4 degrees F700, degree of saponification 99 mol!%) $1 Mugamine In contrast to control example 1, the ethylene film was Lamination property.

Hon vs. Otori 111 & Utehabori Eterenteleph I rate film aigs+*.

Example 2 A: Stretching ratio 9.6 times (ItL 5.2 times, width 5 times),
Thickness 14μ, oxygen permeability 0.5 tl': /lit/
24k r (20℃, 65g6RH), crystallinity 50
G6 polyvinyl alcohol biaxially stretched film (plasticizer usage amount 0, 20 emaa temperature at 210°C after stretching, polyvinyl alcohol polymerization degree 1200, saponification degree 99 mol%) B: Alkali-soluble type acrylic copolymer photoresist film A methyl ethyl lactone solution (B) was applied onto the film using a roll coater and dried. The thickness of B after drying is 9 with 25 tones.

This 21111fi product of A/B was stacked on a copper-clad paper board so that B was fused to the metal surface, and the paper was bonded by heating and pressing at a temperature of 100°C, and then exposed in the same manner as in Example 1. , developed.

The results are shown in No. 211.

Control Examples 4 to 5 In addition to using a polyethylene terephthalate film with a thickness of 25 μm (Control Example 4) and the unstretched polyvinyl alcohol film used in Control Example 2 (Control Example 5), exposure and development were carried out in the same manner as in Overturning 2. went.

The results are shown along with the second decay.

Table 2 Example 3, Comparative Example 6 The following film was used instead of the polyvinyl alcohol biaxially stretched film, and a solvent-soluble acrylic copolymer photoresist was used as the photoresist 8. 9. Conduct experiments in the same way. Furthermore, development #11,
1.1- 8 using a developer consisting of trichloroethane
It lasted 0 seconds.

II5 the result! Shown in E.

Example 5 Stretching ratio: 5.5 times (length: 5.5 times, width: 1 time), thickness: 17N
S oxygen permeability 0.6 cc/j/24kr (20℃,
65%RH), polyvinyl alcohol-axially stretched film with a crystallinity of 4596 (plasticizer usage amount 1%, after stretching 200%
Heat treatment at ℃ for 20 seconds, polymerization degree of polyvinyl alcohol 1
500, saponification degree 99 mol g6) Control example 6 Stretching ratio 1.4 times (Ill, 4 times, width 1 times), thickness 20
μ, oxygen permeability 5.5 cc/vIl/24br (2Q
"C, 65% RB), polyvinyl alcohol-axially stretched film with crystallinity 50g6 (polyvinyl alcohol polymerization degree 1500, saponification degree 99 mol%)

Claims (1)

[Claims] Layer structure consisting of 1.74 lume A/photoresist layer B vt
ta) or a film-containing/photoresist layer B/film C layer structure (b), in the case of G(), leave it as it is; in the case of ←), peel off C and then make contact with the metal 1iKI. In a laminated structure of the type in which A is polymerized and adhered to the film, and A is peeled off and developed after exposure through a film, as film A: 1) the stretching ratio is at least 1.5 times or more uniaxially;
Oxygen transmission rate at 20℃, 651i R11K is 508
/m/24 kr or less, -) A photosensitive laminate structure characterized by using a polyvinyl alcohol stretched film having a crystallinity of 55 or more. 2. Patent Il Ai Range S 1, in which the film A is a polyvinyl alcohol biaxially stretched film with an area magnification of 2.5 times or more
Structures described in Section. 1 The upper KB meeting is the upper layer (C) and the layer structure a (c
4. The structure according to claim 1, wherein the structure comprises: 4. KBt on tC is layered by laminating KAt on Kugo B (b)
2. A structure according to claim 1, which is formed of: