CN100564432C - The manufacture method of foams - Google Patents

Abstract

The present invention relates to be formed with the foams and the manufacture method thereof of independently a plurality of bubbles and/or a plurality of bubbles of successive, especially relate to the manufacture method of foams of the micro bubble of the thickness, shape and the foamy structure that have expectation in the foams of the micro bubble below bubble diameter is 10 μ m.The invention provides a kind of manufacture method that comprises the foams of following operation: irradiation process, to foaminess composition irradiation active energy ray thing, the alkali that described foaminess composition contains the acidic acid producing agent of the effect that utilizes active energy ray or produces alkali produces agent, also contains to have the compound that decomposes the reducing foaming property functional group that discharges more than one lower boiling volatile matter with acid or alkali reaction; And foamed process, in decomposition discharges the temperature province of described lower boiling volatile matter, under pressure-controlling, make the foaming of foaminess composition.

Description

The manufacture method of foams

Technical field

The present invention relates to be formed with the foams and the manufacture method thereof of independently a plurality of bubbles and/or a plurality of bubbles of successive, especially relate to the thickness, shape, and the manufacture method of the foams of the micro bubble of foamy structure that have expectation at bubble diameter in smaller or equal to 10 μ m and foams smaller or equal to the micro bubble of 1 μ m.In addition, the foams that utilize manufacture method of the present invention to obtain are the foams with the high functionality micro bubble that can not obtain in the prior art, promptly relate to following raw material: it not only has the effect of the mechanical strength reduction that suppresses foams, reduce the contraction of forming process product such as injection forming, the effect of warpage, and the effect that improves dimensional stability, and the heat insulating ability of control foam body freely, low electric capacity is forthright, scattering of light, light reflective, sheltering, white, opacity, wavelength selectivity reflection and transmissivity, light weight, buoyancy, sound insulation, sound absorbing, resiliency, damping property, absorptivity, adsorptivity, storage property, perviousness, characteristics such as filterableness.

The right of priority that Japanese patent application 2004-313890 number of the Japanese patent application submission on October 28th, 2004-287977 number 1 of present patent application requirement submission on September 30th, 2004 and the Japanese patent application of submitting on November 25th, 2004 are 2004-340884 number, and with its content introducing present specification.

Background technology

The summary of foams:

Habitual foams are the foams that are made of urethane foam or styrofoam, the such organic materials of foamed polyethylene mostly, also disclose the foams that are made of inorganic materials such as porous ceramics, sintered glasses in addition.In the foams that constitute by organic materials, the porous plastics that with the macromolecular material is matrix is more, and majority has effectively utilized macromolecular material to be liquid when foaming, and has the such characteristic of appropriate viscosity ((promptly with reference to “ development foam Duo Kong Quality Ti Ji Intraoperative と purposes Zhan Open, foams, porous insert technology and purposes are launched) (distribution: East レ リ サ one チ セ Application one is (promptly, Toray-research center), 1996) "; and " Trees Zhi development foam forming Ji Intraoperative is (promptly, the foaming and molding technology of resin) (Ji Intraoperative Qing Reported Association meeting (promptly, technical intelligence association), calendar year 2001) ").

As the characteristic of the foams that utilize the whole bag of tricks to make, can enumerate heat-insulating property, buffering and damping performance, light weight and buoyancy, absorbing performance etc.These useful characteristics are utilized in extensive fields such as pallet, electrothermal sensitive recording paper, wrapping material, surfboard, stereo sets at refrigerator or material of construction, food.In addition, when foams have continuous air bubbles, because surface-area significantly increases, thereby show gas material or fluent material are had absorption property and shelf characteric, carrier property and catalyst performance and penetrating quality and strainability etc., and in home-use sponge, medical separatory membrane etc., be utilized.

In the representational manufacture method of porous plastics, accounted for most though in macromolecular material, sneak into the method for whipping agent, also can adopt following method: utilized method (Japanese patent laid-open 11-238112 communique) that the inside that produced by stretch processing peels off, utilize the method that is separated (Japanese patent laid-open 10-504582 communique) that the cross-linking density difference by macromolecular material produces etc.About the method for sneaking into whipping agent a lot of disclosures are arranged, roughly can be categorized as chemical foaming agent and pneumatogen.

Chemical foaming agent has thermolysis type and photolysis type.Thermolysis type whipping agent carries out discharging after the thermolysis more than one gas, for example nitrogen and carbonic acid gas etc.As chemical foaming agent, known have: with azodicarbonamide, azobis isobutyronitrile etc. is the azo compound of representative, and with p, the two benzene sulfo group hydrazides of p '-oxygen etc. are the organic compound such as sulfonyl hydrazines compound of representative, and mineral compound such as sodium bicarbonate.The foaming that uses thermolysis type whipping agent is whipping agent is mixed or to be dissolved in the temperature range below the decomposition temperature of whipping agent behind the remollescent polymer, is heated to the above temperature range of decomposition temperature of whipping agent, by extensive practicality.Can use auxiliary blowing agent, linking agent, stablizer etc. simultaneously as required.Photolysis type whipping agent by ultraviolet ray, electron rays isoreactivity energy line (radiation) decomposes, thereby for example discharge gas such as nitrogen.Can enumerate p-phenylazide formaldehyde etc. contains the compound of azido-and p-diazonium pentanoic etc. and contains diazo compound.The foaming that uses the photolysis whipping agent is to make its foaming by the energy line irradiation, or makes the method for its foaming at the irradiation post-heating.In addition, usually, chemical foaming agent is also included within the organic compound that produces gas in the high molecular polymerization process, and its representative materials can be enumerated urethane etc.Urethane is the polymkeric substance of polyvalent alcohol (have two above alcoholic hydroxyl promptly-oligomer of OH base) and polyisocyanate the fat material of NCO base (have two above isocyanatos in the molecule to be-), produces CO in polymerization process ₂Gas and form foams.

As pneumatogen, can enumerate that for example butane and pentane etc. are the volatility saturated hydrocarbons material of representative and are that the volatility of representative is fluoridized hydrocarbons etc. with fluoroethane etc. with the lower boiling volatile matter.As pneumatogen, using mostly volatilizees down at 50～100 ℃ as liquid at normal temperatures becomes the lower boiling volatile matter of gas, they are impregnated in the macromolecular material under its temperature below boiling point, be heated to the above temperature of boiling point of pneumatogen again, thereby can form foams.In addition, for also can be used as pneumatogen, gasiform rare gas element, for example carbonic acid gas and nitrogen etc. use at normal temperatures and pressures.At this moment, make to be in the macromolecular material that the gasiform rare gas element is dissolved in the molten state that is controlled to be suitable pressure and temperature, then this mixing system is exposed under the state of normal temperature and pressure, thereby fluent meterial gasifies rapidly, expands and obtains foams.As other whipping agent, known also useful thermoplastic macromolecule material is made shell, the lower boiling volatile matter is sealed in its inner and capsule shape whipping agent that make.

In recent years, the people such as N.P.Sshu of Massachusetts Polytechnics (Massachusetts Institute of Technology) have proposed a kind ofly to contain the foams of micro bubble, promptly be called as the material of cellular plastic (MCP), it is characterized in that: bubble diameter is 0.1～10 μ m, and bubble density is 10 ⁹～10 ¹⁵Individual/cm ³(No. 4473665 communique of United States Patent (USP)).Gazed at as the new foam that possesses the structure that does not have at present, in various research institutions all in the research of actively carrying out MCP.It was reported, can realize by fine foamed: the effect that the mechanical strength that suppresses to be caused by foaming reduces reduces the contraction of forming process product such as injection forming, the effect of warpage, and improves dimensional stability.

Manufacture method at this cellular plastic is in the MCP foaming, under high pressure or under the supercritical state, inactive gass such as carbonic acid gas, nitrogen are impregnated into it is reached capacity, reduce pressure then and heat, thereby obtain cellular plastic.Because the miniaturization of bubble is to realize by the degree of supersaturation that raising is dissolved in the rare gas element in the resin, so this MCP foaming adopts high-pressure impregnation and obtains higher saturated pickup when gas impregnated, thereby the time discharge this pressure and obtain higher degree of supersaturation in foaming.Usually, low temperature, Gas Solubility is just high more, so but to form bubble diameter be the interrupter method that the following fine foam of 10 μ m can adopt the normal temperature high voltage dipping.Exist in the interrupter method gas reach capacity need longer dipping time problem.For example, it was reported, make carbonic maceration in the polyethylene terephthalate to several days time of saturated needs, cause the inefficient problem of making.In order to shorten the dipping time of rare gas element, use the material that floods easily then just can deal with problems at once.But, in the reverse side of the character of flooding easily, in case have the character that escape also takes place the gas of dipping easily.Therefore, even realized the shortening of dipping time, a part that is impregnated into the gas in the plastics under high pressure conditions is before foaming by the decompression operation, the escape of gas phenomenon that generation is spread in large quantities from frosting, so be difficult to obtain the high degree of supersaturation that can effectively foam, thereby be difficult to realize the bubble miniaturization.Interrupter method has been absorbed in the predicament on the ultimate principle in bubble miniaturization and low the manufacturing between the efficient.High injection or the extrusion molding of making efficient also arranged in the MCP foaming.In cylinder, the rare gas element of supercritical state is imported in the resin of molten state and carries out mixingly, make its dissolving, with interrupter method relatively because the gas impregnated time is short, and adopts continuous manufacture, so make the efficient height.But, in foamed process, keep high hypersaturated state to be difficult to, bubble diameter is reached be considered to below tens micron orders difficulty.Can think that the reason that the amount of inert gas that can flood in the high temperature dipping tails off is, foam that so gas is escaped easily, or bubble is grown up easily because viscosity is low owing to pass through the fusion condition of high temperature.Therefore, be that purpose obtains below the thickness 100 μ m by the MCP foaming and the foams below the bubble diameter 1 μ m are difficult with the practicality.

Recently, the inventor has invented light acid, the alkali method that reduces foaming, it is characterized in that, can obtain the foams of micro bubble easily, be that bubble diameter is the following ultramicropore plastics (SMCP) of 1 μ m, can be made into thickness is the following slim foams (the Japanese Patent spy opens the 2004-2812 communique) of 100 μ m.This foaming has adopted the foaminess composition that utilizes active energy ray and heat to foam.The alkali that the foaminess composition contains by acidic acid producing agent of active energy ray effect or generation alkali produces agent, and, contain and have the reducing foaming property compound that more than one lower boiling volatile matter is decomposed the reducing foaming property functional group that breaks away from acid or alkali reaction.

(problem 1)

Can find out easily, in light acid, alkali reduce foaming method,, can obtain to have the foams of the foamy structure of expectation freely by the design of foaminess composition or the illuminate condition and the heating condition of active energy ray are controlled.But, when under normal pressure, foaming, have following situation: different to be difficult to obtain bubble diameter be below the 1 μ m and thickness is slim SMCP below the 100 μ m according to the kind of foaminess composition, and the distortion that produces because of foaming is excessive is difficult to keep the foaming shape expected.In addition, also have following situation: being difficult to make bubble diameter is below the 1 μ m and thickness is the SMCP of the above thick type of 100 μ m; Be difficult on base material and substrate, form foams, be difficult to form foams with two-layer above laminated multi-layer structure, and be difficult to form sheet, membranaceous, fibrous and bar-shaped etc. be not foams fairly simple, complicated shape.

About inhomogeneous foams:

The equally distributed even foams of bubble diameter and bubble density are got the foaming character which part in the foam all has same degree.In contrast, the foaming character of the distribution of bubble diameter or bubble density heterogeneity foams different with the position also distributes according to its bubble and different.So people's expectation has the functional of the irrealizable height of homogeneity foams.

As inhomogeneous foams, for example can enumerate: bubble distribute the inclined foam be successive or interim slope, on part, alternatively dispose the part foams of not foamed zones and foamed zones etc.

Inhomogeneous foams are thick closely to change and obtain with the position by what the control foamed state made the size of bubble diameter or bubble density.All the time, people attempt adopting various chemical blowing processs, the acquisition of physical blowing method to have the inhomogeneous foams of the bubble distribution of expectation.

As the manufacture method of the inhomogeneous foams that utilize chemical blowing process, for example can enumerate: the manufacture method of putting down in writing in No. 3422384 communique of Japanese patent laid-open 5-72727 communique or Japanese Patent.In Japanese patent laid-open 5-72727 communique, following method is disclosed: by being impregnated with the polymeric film of light foaminess compound such as diazonium compound with the irradiation of the interference light of argon laser, the highlights foaming of interference fringe and dark portion does not foam.

In addition, No. 3422384 communique of Japanese Patent announced following method: by photomask the coating layer that contains thermally foamable compound and optical polymerism compound is carried out UV-irradiation and heating, from but not irradiation portion foaming, and the foaming that the reason polymerization of irradiation portion produces suppresses effect and does not foam.

These methods come foamed state is controlled by the control exposure intensity.The manufacture method of these foams increases because of the pickup that can make rare gas element, thereby can form a large amount of micro bubbles.

As the example of making inhomogeneous foams by this manufacture method, can enumerate: Japanese patent laid-open 11-80408 communique or Japanese Patent spy open disclosed manufacture method in the 2002-363324 communique.In Japanese patent laid-open 11-80408 communique, in the saturated operation of gas, make the dipping concentration of rare gas element form.In addition, open in the 2002-363324 communique, in foamed process, be impregnated with the pros and cons of the sheet material of gas with the differing temps heating the Japanese Patent spy.

(problem 2)

But above-mentioned which kind of method all can not be controlled bubble density, bubble pattern etc. freely.

About light guide:

Light guide is the optics that incident light is penetrated along the direction different with its incident direction.Light guide is that the shaping thing by light transmission constitutes, and on its surface or the inner emergent light pattern that specific refractory power is changed that is provided with.

As obtaining this emergent light method of patterning, can adopt: (1) prints the method for white point from the teeth outwards; (2) be shaped the from the teeth outwards method of working groove or point; (3) in the method for inner dispersed light scattering object.

The scattering of light light guide that adopts the method for (3) is to make the incident light scattering and to the light guide of the mode of light-emitting face guiding by the light-scattering body that inside exists.On the light guide surface, do not carry out image processing,, do not need light diffusion sheet, have the advantage that to save parts so compare with the shaping light guide of the method for the printing light guide of the method that adopts (1) or employing (2).In addition, can make the light-weighted advantage of light guide by using the little light-scattering body of proportion, also having.

As light-scattering body, for example can use: the vinylbenzene particulate described in the Japanese patent laid-open 06-324215 communique, pearl silicon described in the Japanese patent laid-open 10-183532 communique, iso-butylene micropartical described in the Japanese patent laid-open 11-19928 communique, light diffusing particles such as the hollow pearl described in the Japanese patent laid-open 9-17221 communique, bubble that forms by carbonic acid gas described in the Japanese patent laid-open 11-291374 communique etc.

When in surface illuminating device, using the scattering of light light guide, in order to penetrate uniform light from light-emitting face, from needing to improve scattering of light more away from light source is far away more.But it is difficult that the particle diameter of light-scattering body or density distribution are changed in reality.Therefore, light-scattering body only is to make its homodisperse, and whole light guide is configured as more away from the thick more wedge shape of light source (formation cone angle).

To this, a kind of emptying aperture diameter and density of making has been proposed along with become the earth disperse, hollow particle, light guide (Japanese patent laid-open 06-324215 communique) away from light source to reduce brightness disproportionation.

For the light that prevents the scattering of light light guide leaks and improves outgoing efficient, need block face except the plane of incidence or exit facet with reflector.And, other opticses such as prism need be set on the exit facet of light guide under the more situation.

Therefore, without light diffusion sheet, but a plurality of opticses are used in combination in the existing scattering of light light guide, and in the framework of box-shaped overlapping for example reflector plate, light guiding plate, the prism etc. taken in.

Light guide mainly is built in the surface illuminating device of edge light mode.The surface illuminating device of this edge light mode can be used in the general set lights or display unit.

For example, because the liquid crystal of display element itself does not have luminous in the liquid crystal indicator, so with the surface illuminating device of back light that is called as edge light mode or headlight and with just showing its Presentation Function.Follow the variation of the purposes of liquid crystal indicator etc., to the strictness that also becomes of the desired quality project of light guide.

Particularly space-savingization and the portability owing to display unit comes into one's own, and also carrying out miniaturization as the LED of light source use, so the slimming of light guide and lightweight are also by strong request.Because light guide has accounted for the over half of surface illuminating device thickness, so people expect its slimming very much.In addition, in order to improve display quality and to realize power saving, also require to improve the utilising efficiency of light.

But,, need whole light guide be configured as wedge shape according to above-mentioned for the light guide of dispersed light scattering object equably only.Specifically be to be shaped by injection forming, but because thin more, filling ratio in mould or transfer printing precision being just poor more, is difficult so be configured as the following wall thickness of 1mm.

To this, as described in patent documentation 6, hollow-particle is disperseed make its emptying aperture diameter and density along with the light guide that increases away from light source in, also can make tabular, therefore think and carry out slimming easily.But record does not form the such emptying aperture diameter and the concrete dispersing method of density distribution, does not in fact make the method for such light guide yet.

(problem 3)

No matter in above-mentioned which kind of method, all there is restriction in the slimming of scattering of light light guide.

In addition, when in by the overlapping framework that is accommodated in box-shaped, constituting the scattering of light light guide, only take in to make and produce the gap between each optics, can not suppress light fully and leak reflector plate, light guiding plate, prism etc.Therefore, improve the light utilising efficiency and also have restriction.In addition, owing to using a large amount of parts to constitute, so the productivity aspect also has problems.

Summary of the invention

One of problem to be solved by this invention is that easy foams to micro bubble foam and control and shape control in light acid, alkali reduce foaming method.Especially bubble diameter is the foams of the following and even micro bubble that 1 μ m is following of 10 μ m, can be easily and control stably have the foamy structure and the shape of foams of the micro bubble of expectation thickness, shape and foamy structure.

In view of the foregoing, two of problem to be solved by this invention be: provide a kind of and be limited in bubble diameter in the fine scope and can obtain high bubble density zone and can be arbitrarily and obtain the manufacture method of the inhomogeneous foams that the bubble of a lot of patterns such as for example three-dimensional bubble distribution distributes easily.

In view of the foregoing, three of problem to be solved by this invention be: provide by realizing that slimming, integrated, parts simplify surface illuminating device, display unit and the means of illumination that improves light utilising efficiency and productive light guide and manufacture method thereof simultaneously and use this light guide.

In order to address the above problem, the structure of the present invention adopts following (1)～(9).

(1) comprises the manufacture method of the foams of following operation: irradiation process, utilize active energy ray irradiation foaminess composition, the alkali that described foaminess composition contains the acidic acid producing agent of the effect that utilizes active energy ray or produces alkali produces agent, also contains to have the compound that decomposes the reducing foaming property functional group that discharges more than one lower boiling volatile matter with acid or alkali reaction; And foamed process, in decomposition discharges the temperature province of described lower boiling volatile matter, under control pressure, foam.

(2) according to the manufacture method of foams of above-mentioned (1) record, it is characterized in that, comprise forming process, in foamed process or before arbitrary the time photoetching form foaminess composition.

(3) according to the manufacture method of foams of above-mentioned (2) record, it comprised forming process before irradiation process.

(4) according to the manufacture method of foams of above-mentioned (2) record, it is characterized in that, between irradiation process and foamed process, comprise forming process.

(5) according to the manufacture method of foams of above-mentioned (2) record, it is characterized in that foamed process and forming process are carried out simultaneously.

(6) a kind of manufacture method of foams, it is characterized in that, has foamed process, in described foamed process, produce agent, also contain foaminess composition and discharge the temperature province internal radiation active energy ray of described lower boiling volatile matter to the alkali that contains the acidic acid producing agent of the effect that utilizes active energy ray or produce alkali, under pressure-controlling, make its foaming simultaneously in decomposition with the compound that decomposes the reducing foaming property functional group that discharges more than one lower boiling volatile matter with acid or alkali reaction.

(7) a kind of manufacture method of foams is characterized in that, according to arbitrary invention in (1)～(6), while comprise after foamed process and carry out pressure-controlling refrigerative operation.

(8) a kind of manufacture method of inhomogeneous foams, it is characterized in that, in the manufacture method of foams of above-mentioned (3) record, any in the and the following forms predetermined uneven distribution more than one: (a) the radioactive rays energy that the molding that is shaped by the preliminary forming operation is applied; (b) heat energy that molding is applied by the foams forming process; (c) the reducing foaming property functional group concentration in the molding; (d) acid producing agent in the molding or alkali produce the concentration of agent.

(9) light guide of the inhomogeneous foams of use above-mentioned (8) record.

The present invention has following advantage: at bubble diameter is below the 10 μ m even in the foams of the micro bubble below 1 μ m, can be easily and stably realize thickness with expectation, shape, and the foamy structure control and the shape control of the foam of the micro bubble of foamy structure.In addition, the foams of the high functionality micro bubble that does not have in the prior art of Huo Deing have following advantage like this: not only have the low effect of the mechanical strength of inhibition, alleviate the contraction of forming process product such as injection forming, the effect of warpage, and the effect that improves dimensional stability, and can easily make the luminous reflectance scattering properties of control foam body freely, dielectric characteristic, and the raw material of insulating characteristics etc., and at wrapping material or material of construction, medical material, electric material, electronic information material, automotive materials etc. play great role in the various fields.In addition, can provide a kind of follows the bubble distribution also to produce the high functionality foams that foaming character distributes in above-mentioned various uses.And, can make the light guide of liquid crystal indicator etc. by simple manufacturing process.

Description of drawings

Fig. 1 is the explanatory view that adopts the pressure controling method (controlled function very close to each other) of plate.

Fig. 2 is the explanatory view that adopts the pressure controling method (controlled function very close to each other) of mould.

Fig. 3 is the explanatory view that adopts the pressure controling method (gapped controlled function) of plate.

Fig. 4 is the explanatory view that adopts the pressure controling method (gapped controlled function) of mould.

Fig. 5 is the cross sectional photograph of the foams of embodiment 1.

Fig. 6 is the cross sectional photograph of the foams of embodiment 2.

Fig. 7 is the explanatory view that adopts the pressure controling method (refrigerating function is arranged) of mould.

Fig. 8 is the cross sectional photograph of the foams of comparative example 1.

Fig. 9 A is the schematic perspective view of the mutual foaming of expression.

Fig. 9 B is the position, the left and right sides on the section of presentation graphs 9A and the chart of the relation between the bubble diameter.

Figure 10 A is the schematic perspective view of the mutual foaming of expression.

Figure 10 B is the position, the left and right sides on the section of presentation graphs 10A and the chart of the relation between the bubble diameter.

Figure 11 A is the schematic perspective view of expression continuous tilt foaming.

Figure 11 B is the position, the left and right sides on the section of presentation graphs 11A and the chart of the relation between the bubble diameter.

Figure 12 A is the schematic perspective view of expression continuous tilt foaming.

Figure 12 B is the position, the left and right sides on the section of presentation graphs 12A and the chart of the relation between the bubble density.

Figure 13 A is the schematic perspective view of the interim inclination foaming of expression.

Figure 13 B is the position, the left and right sides on the section of presentation graphs 13A and the chart of the relation between the bubble diameter.

Figure 14 A is the schematic perspective view of the interim inclination foaming of expression.

Figure 14 B is the position, the left and right sides on the section of presentation graphs 14A and the chart of the relation between the bubble density.

Figure 15 has utilized the explanatory view that makes the modulator approach of the different inclined foam of the arrival amount of radioactive rays energy by depth of penetration.

Figure 16 is the explanatory view of modulator approach that has utilized the part foams of photomask.

Figure 17 is the explanatory view of modulator approach that has utilized the inclined foam of photomask.

Figure 18 has utilized the explanatory view of modulator approach of adjusting the inclined foam of irradiation time by the slide plate of photomask.

Figure 19 is the mode chart of inclined foam that has utilized the Heating temperature difference at the outside surface and the back side.

Figure 20 has utilized the mode chart of hot record with the part foams of printer.

Figure 21 has utilized the mode chart of hot record with the inclined foam of printer.

Figure 22 is the mode chart that has utilized the inclined foam of a plurality of foaminess compositions that structure has nothing in common with each other.

Figure 23 is the mode chart that has utilized the part foams of a plurality of foaminess compositions that structure has nothing in common with each other.

Figure 24 is the photo by the foams of embodiment 7-1 acquisition.

Figure 25 is the photo of expression by the foamy structure of the uviolizing portion of the foams of embodiment 7-1 acquisition.

Figure 26 is the photo by the foams of embodiment 7-2 acquisition.

Figure 27 is the photo by the foams of embodiment 7-3 acquisition.

Figure 28 is the photo of expression by the foamy structure on a～e point of the foams of embodiment 7-3 acquisition.

Figure 29 is that expression is by the bubble diameter on a～e point of the foams of embodiment 7-3 acquisition and the chart of bubble occupied area rate.

Figure 30 is the stereographic map of first embodiment of expression light guide of the present invention.

Figure 31 is the manufacture method example of first embodiment of light guide of the present invention.

Figure 32 is other examples of manufacture method of first embodiment of light guide of the present invention.

Figure 33 is the stereographic map of second embodiment of expression light guide of the present invention.

Figure 34 is the stereographic map of the 3rd embodiment of expression light guide of the present invention.

Figure 35 is the manufacture method example of the 3rd embodiment of light guide of the present invention.

Figure 36 is the stereographic map of the 4th embodiment of expression light guide of the present invention.

Figure 37 is the stereographic map of the 5th embodiment of expression light guide of the present invention.

Figure 38 is the stereographic map of the 6th embodiment of expression light guide of the present invention.

Figure 39 is the stereographic map of the 7th embodiment of expression light guide of the present invention.

Figure 40 is the stereographic map of the 8th embodiment (surface illuminating device) of expression light guide of the present invention.

Figure 41 is the explanatory view of manufacture method of the 8th embodiment (surface illuminating device) of light guide of the present invention.

Figure 42 is the explanatory view of manufacture method of the 8th embodiment (surface illuminating device) of light guide of the present invention.

Figure 43 is the stereographic map of the 9th embodiment (surface illuminating device) of expression light guide of the present invention.

Figure 44 is the explanatory view of manufacture method of the 9th embodiment (surface illuminating device) of light guide of the present invention.

Figure 45 is the explanatory view of manufacture method of the 9th embodiment (surface illuminating device) of light guide of the present invention.

Figure 46 is the stereographic map of the tenth embodiment (surface illuminating device) of expression light guide of the present invention.

Figure 47 is the explanatory view of manufacture method of the tenth embodiment (surface illuminating device) of light guide of the present invention.

Figure 48 is the explanatory view of manufacture method of the tenth embodiment (surface illuminating device) of light guide of the present invention.

Figure 49 is the explanatory view of manufacturing processed of the embodiment of expression light guide of the present invention.

Nomenclature

P1 foaminess composition (tabular)

P2 pressure-controlling plate (function is adjusted in no gap)

The P3 pressure-controlling patrix of mould

The P4 pressure-controlling counterdie (function is adjusted in no gap) of mould

P5 pressure-controlling plate (gapped adjustment function)

The P6 pressure-controlling counterdie (gapped adjustment function) of mould

P7 gap adjustment function portion

P8 water coolant introduction part

P9 water coolant discharge portion

1 molding

2 photomasks

3 peristomes

The M matrix

The B bubble

10 light guiding sections

13 low foamed zones

14 high foamed zones

Foamed zones in 15

Embodiment

Manufacture method of the present invention comprises: active energy ray is shone the irradiation process of foaming composition and at the lower boiling volatile matter operation that the temperature province inner control pressure that discharges makes its foaming takes place to decompose from the foaminess composition.When foaming,, can easily control foams foamy structure and shape by control pressure when lower boiling volatile matter generation decomposition release.

In the present invention,, can after irradiation process, carry out foamed process, also can when carrying out foamed process, shine as active energy ray irradiation process and the relation between the operation that foams under the control pressure.

In order stably to obtain to have the foams of expecting thickness, shape, reaching the micro bubble of foamy structure, manufacture method of the present invention can comprise forming process.Forming process can be categorized as preliminary forming operation and foams forming process.So-called preliminary forming operation is meant following operation: forming process that is provided with by the front and back in the operation of irradiation active energy ray and the operation that is shaped in irradiation, making the resin before the foaming is that the foaminess composition is shaped.So-called foams forming process is meant following operation: the temperature province that discharges the lower boiling volatile matter in decomposition is carried out pressure-controlling, thereby while foam and be shaped; Perhaps after foaming with the foaming ester moulding.

In foamed process, the temperature of foaminess composition is high more, and it is fast more that the lower boiling volatile matter decomposes the speed of response that discharges, so the easy more miniaturization of bubble.But, when the glass transition temp of the foams resin after the foaming was low, if keep after foamed process under the pyritous state pressure release, then following situation may take place: bubble was grown up and even is integrated, cause bubble diameter to increase always, can not keep micro bubble; Or, can not obtain the foams of intended shape because foaming increases the distortion multiplying power.In this case, on one side comprise after the foamed process of control pressure that preferably control pressure carries out the refrigerative operation on one side.As method of cooling, that can enumerate has: the structure that makes flow of cooling water is set in the pressurized, heated position of squeezing machine and shaping dies, utilizes water-cooled to carry out the refrigerative method; And use semiconductor element to carry out electric pressure refrigerative method etc.

The operation of the manufacture method of foams of the present invention is not limited to this, except that these, can apply various operations to the part of suitable expectation.For example, also can suitably import operations such as stretching process, clean operation, drying process and buffering operation.Manufacture method of the present invention also can be combined by these operations, and each operation is made up discontinuously or continuously, perhaps plural at least operation is set at the operation of carrying out simultaneously.Which kind of method can in interrupter method or the continuous processing.And in the manufacture method of foams of the present invention, because can form the intensity distribution of active-energy, the intensity distribution of heat energy, the concentration distribution of foaming composition etc., thus the control that also can acquisition relevant with bubble diameter or bubble density bubble distributes can change arbitrarily and have foams that bubble distributes.Below the concrete example of each operation is described, but the present invention is not limited only to this.

At first, thus the operation of carrying out the pressure-controlling foaming in the temperature province that decompose to discharge from the foaminess composition at the lower boiling volatile matter is described.As the example of pressure controling method, can be listed below method etc.: part opposed faces compress control method, as shown in Figure 1, use two plates only to pressurize and carry out pressure-controlling from opposed; Whole surface pressure control method as shown in Figure 2, uses mould to pressurize and carry out pressure-controlling from whole.In addition, also has following type: as shown in Figures 1 and 2, under the situation of controlled function very close to each other, can change the type of pressure according to thrust pressure; And the type of the gapped controlled function shown in Fig. 3 and Fig. 4 etc. etc.In whole surface pressure control method, that can enumerate has: fluid such as injecting gas, liquid, molten mass in close die and carry out pressure controlled method; Utilize because self bulging force of the foams that the foaming composition foaming produces and the pressure by generation gas carry out pressure controlled method; Utilize the thermal expansion force of mould or mould inner stuffing to carry out pressure controlled method etc.

The scope of the preferred 0.1MPa～20MPa of pressure, the scope of especially preferred 0.5MPa～10MPa.

Decompose the temperature province that discharges in order to form the lower boiling volatile matter, can utilize well heater to heat, utilize its waste heat in the time of perhaps can in last operation, heating.What is called lower boiling volatile matter is meant the temperature province of following scope from the temperature province of foaminess composition decomposition release: than the minimum temperature height of lower boiling volatile matter generation decomposition release, and also lower than the temperature of various rerum naturas such as the decomposition temperature of not damaging lower boiling volatile matter generation decomposition release resin (being the foams resins) afterwards or intensity.This temperature province changes according to the kind of foaming shape composition.For example, for acrylic acid series foaminess composition, decompose the minimum temperature that discharges and be approximately 75～85 ℃, the decomposition temperature of foams resin is approximately 180～200 ℃; For polystyrene foaminess composition, minimum temperature is approximately 65～80 ℃, and the decomposition temperature of foams resin is approximately 160～180 ℃.Temperature during foaming is high more, and the decomposition release rate of its lower boiling volatile matter is fast more, and the easy more increase of degree of supersaturation, can think preferred concerning the bubble miniaturization significantly.But, high temperature, resin viscosity is just low more, grows up and is integrated and bubble is just easy more, expands thereby become.Therefore, have the temperature province that is suitable for foaming.This zone is different and different with the kind of foaminess composition, is 65～200 ℃, is preferably 90～180 ℃, more preferably 100～160 ℃.

Be not particularly limited as well heater, can exemplify: well heater that can heat by conduction heating, resistive heating, induction heating (and microwave heating), infrared heating etc.That can enumerate has: utilize the infrared drier of electric or combustion type of radiation heat or the hot air dryer etc. that utilizes the roller heater of electromagnetic induction, the oil heater that utilizes oily media, electrothermal heater and utilize the hot blast of above-mentioned well heater.In induction heating or infrared heating, because be to the direct-fired inner type of heating of material internal, so can carry out than outside heating methods such as hot air dryer even heating more rapidly, but need suitably to select to be used for the material of pressure controlled plate or mould.When being induction heating, frequency of utilization is 1MHz to the 300MHz (high-frequency energy of wavelength 30m～1m).The frequencies of using 6MHz to 40MHz more.In induction heating, especially microwave heating, frequency of utilization is 300MHz (microwave of wavelength 1m～1mm) uses 2450MHz and 915MHz (identical with microwave oven) more to 300GHz.When being infrared heating, the wavelength that utilizes region of ultra-red is the hertzian wave of 0.76～1000 μ m.Wait from heater table surface temperature and material-to-be-heated infrared absorption spectra, the suitableeest frequency band of the wavelength of selecting according to situation changes, but can preferably use the ripple of 1.5～25 μ m, the more preferably wave band of 2～15 μ m.

Below the operation with active energy ray irradiation foaming composition is described.As the active energy ray that uses among the present invention, that can enumerate has, ionization radioactive rays such as electron rays, ultraviolet ray, visible rays, gamma-rays etc.Below, prove the situation of radioactive rays in addition.Wherein preferably use electron rays and ultraviolet ray.

When using the electron rays irradiation, in order to obtain sufficient transmission power, using acceleration voltage is the electron rays accelerator of 30～1000kV, and preferably uses the electron rays accelerator of 30～300kV, preferably one-pass absorption light amount is controlled to be 0.5～20Mrad (1rad=0.01Gy).If acceleration voltage or electron rays irradiation dose are lower than above-mentioned scope, then the transmission power of electron rays is insufficient, can not be injected into the inside of molding fully, in addition, if excessively greater than this scope, energy efficiency is worsened, and the molding undercapacity that is obtained, resin and additives decompose that its inside comprises take place, and the quality of the foams that obtained can not be met the demands.As the electron rays accelerator, can use in for example electronics heavy curtain system scan type, the two sweep types etc. any one.When carrying out the electron rays irradiation, if oxygen concn is too high in the irradiation environment, then may hinder acid or alkali generation, with and/or the curing of solidified nature decomposability compound, therefore, preferably replace air in the irradiation environmental gas with rare gas elementes such as nitrogen, helium, carbonic acid gas.Oxygen concn is preferably below the 1000ppm in the irradiation environmental gas, and for electron gain ray energy stably, more preferably it is suppressed at below the 500ppm.

During irradiation ultraviolet radiation, can use normally used ultraviolet lamp in semi-conductor, photoresist material field or ultraviolet curing field etc.Usually as ultraviolet lamp, halogen lamp, halogen heating lamp, xenon short-arc lamp, xenon flash lamp, extra-high-pressure mercury vapour lamp, high pressure mercury vapour lamp, Cooper-Hewitt lamp, middle medium pressure mercury lamp, dark UV lamp, metal halide lamp, inert gas florescent lamp, krypton arc lamp and excited quasi-molecular lampbulb etc. are for example arranged, in recent years, the gamma ray lamp that a kind of emtting electrode short wavelength (peak value 214nm) also occurred.In these lamps, the lamp that produces the less ozone free type of ozone is arranged also.These ultraviolet rays can be scattered lights, also can be the high directional lights of rectilinear propagation.In order accurately to form the part foam, preferred parallel light.In addition, when carrying out uviolizing, also can use: ArF excimer laser, KrF excimer laser and utilization contain various laser apparatus such as the unitary YAG laser apparatus of nonlinear optics crystalline higher harmonics; And ultraviolet LED.As long as the emission wavelength of UV-lamp, laser apparatus and ultraviolet LED is the foaminess that does not hinder the foaminess composition, do not have particular determination, but preferably preferably can make light acid producing agent or light alkali produce the emission wavelength that agent produces acid or alkali efficiently.That is, preferably produce the emission wavelength of the wavelength photoreceptor region overlapping of agent with employed smooth acid producing agent or light alkali.And more preferably emission wavelength and these generation agent are overlapping at the very big absorbing wavelength or the maximum absorption wavelength in wavelength photoreceptor zone, produce efficient thereby improve easily.Ultraviolet energy exposure intensity suitably determines according to the foaminess composition.Variously during as the high UV-lamp of the exposure intensity of representative, can boost productivity, when using long arc lamp, more than the preferred 30W/cm of its exposure intensity (lamp output) using with mercuryvapour lamp, metal halide lamp etc.Ultraviolet cumulative exposure light quantity (J/cm ²) be the product of energy exposure intensity and irradiation time, be bubble distribution and suitable the decision according to foaming composition and expectation.Also can set according to the specific absorbance of acid producing agent or alkali generation agent.In order to stablize and to make continuously, preferred 1.0mJ/cm ²～20J/cm ²Scope.When using UV-lamp, because the exposure intensity height, so can shorten irradiation time.When using excited quasi-molecular lampbulb or excimer laser, though a little less than its exposure intensity, since roughly close with single light, so, can realize higher generation efficient and foaminess as long as make emission wavelength be suitable for producing the wavelength photoreceptor of agent most.When the irradiation light quantity is more, because the UV-lamp heating hinders foaminess sometimes.Can carry out this moment such as the cooling process of cold reflector etc.

Forming process included in the manufacture method of the present invention is described.As moulding method used in the forming process,, can select to be coated with shaping, extrusion molding, injection forming, injection molded, squeezing shaping etc. according to the shape of wanting to be shaped.The resin shape that obtains by forming process does not have particular determination, can suitably determine according to the application target of foams.The object etc. that flap (comprising film like), fibrous material, club is arranged, have the shape of other expectations except above-mentioned shape that can enumerate.Flap can be independent flap or be bonded in lamella on the support, also can be a plurality of by the resin laminated structure that forms.

Example as the coating shaping, can be listed below method etc.: after using dispense tip to be coated with the foaminess composition on the support, if the solution that forms with dilution foaminess compositions such as solvents, then remove solvent composition, on support, obtain the lamella that forms by the foaminess composition with drying machine.At this moment, by peeling off lamella, can obtain the independent flap that forms by the foaminess composition from support.That can enumerate in the coating method has: rod (bar) formula coating method, air doctor blade (air doctor) coating method, blade (blade) coating method, the extruding type coating method, the airblade coating method, the print roll coating method, intaglio plate is coated with Butut, move the film coating method, the Comma coating method, level and smooth coating method, miniature intaglio plate coating method, the reverse roll coating method, the multi roll coating method, dipping formula coating method, the rod-type coating method, the kiss-coating method, door print roll coating method, the canopy coating method, the ramp type coating method, spray (fountain) formula coating method, and slit die formula coating method etc.As having that support can be enumerated: paper, synthetic paper, plastic resin sheet, tinsel and metal evaporation sheet etc., these supports can use separately, perhaps also use behind the lamination mutually.As having that the plastic resin sheet for example can be enumerated: polystyrene resin sheet, polyolefin series resin sheets such as polyethylene, polypropylene, common plastics sheets such as polyester based resin sheet such as polyethylene terephthalate; And engineering plastics sheet such as polyimide resin sheet, ABS resin sheet, polycarbonate resin plate etc.In addition, can enumerate aluminium and copper etc. as the metal that constitutes tinsel.Can enumerate aluminium-vapour deposition sheet, golden evaporation sheet and silver-colored evaporation sheet etc. as the metal evaporation sheet.

As extruding formation method, that can enumerate has: use the general extruding formation method of volution extrusion axis (screw rod), the piston extruding formation method of use piston-like extrusion axis etc.

Example as injection forming, except common ejection forming method, that can enumerate has: vacuum is filled moulding method, ejection compress moulding method, high-speed vacuum filling moulding method, gas absorption melt-shaping method, die temperature cold cycling moulding method, low pressure low speed filling moulding method, injection squeezing moulding method, multiple mould moulding method etc.As the be shaped method of development of the high transferring rate of and fine shape thin molded to nearest popular, that can enumerate has: heat insulating mold moulding method, injection speed be the ultra-high speed injection molding method of 1000～2000mm/sec, be dissolved into rare gas elementes such as carbonic acid gas or nitrogen in the molten resin under supercritical state and do not make the injection molding method that utilizes supercutical fluid that its foaming promptly is shaped etc.

Example as injection molded, can be listed below method etc.: will contain the monomeric liquid foam composition of active energy ray-curable and be injected in the flaky mould of prismatic, the irradiation active energy ray makes its sclerosis, the demoulding then, thus obtain the sheet-like formed thing of prismatic.Resin solidification can take place and produce agent by acid and alkali to produce acid and alkali in illuminate conditions such as light source by suitable selection active energy ray and wavelength simultaneously.

As mentioned above, forming process can be divided into the foam forming process that the foamex after making the preliminary forming operation that the foaminess composition as the resin before the foaming is shaped and making foaming is shaped.Can adopt in the preliminary forming operation will be the net shape of foams or the method for the shape close with it as the foaminess composition direct forming of raw material, also can adopt to be configured as earlier sheet, bar-shaped, ball shape, more simple shape such as Powdered temporarily, be configured as to the multistage method of foams net shape or the shape close again with it.No matter which kind of method can suitably adopt above-mentioned manufacturing process.

As the foams forming process, be included in that control pressure makes its foaming and operation that is shaped and the operation that behind foamed process foams is shaped in the temperature province that the lower boiling volatile matter decompose to discharge.In the former operation that foams simultaneously and be shaped,, also comprise the mold-in injection moulding method and in shaping dies, carry out active energy ray irradiation and temperature, pressure controlled method etc. simultaneously except above-mentioned manufacturing process.

Example as the foams moulding method that adopts the mold-in injection moulding method, can be listed below method: the foaminess composition layer that on Ag evaporation sheet, forms 50 μ m by coating, to be fixed on the predetermined position in the shaping dies by the sheet of active energy ray irradiation, resin injection forming in described forming that the compound by the decomposability functional group with described foaminess composition is constituted.The foams that obtained are for having the thin-walled foaming layer and the optics of foamed resin layer not on Ag evaporation sheet.Foaminess composition on the Ag sheet foams under the state with the temperature heating of the molten resin of cylinder injection and pressurization.Though the shaping dies of the mold-in injection shaping usefulness of using in the foams forming process has no particular limits, compare with the moulds such as steel, aluminium alloy system and stainless steel of normal use, preferably use the higher adiabatic shaping dies of heat insulating ability.As adiabatic shaping dies, can enumerate: the mould that is called as heat insulating mold that is embedded with low thermal conductivity material on the surface of mould.Burying material underground can enumerate: polyimide, HDPE, glass and silica glass, phenolic resin, Zr pottery etc.The reasons are as follows of the adiabatic shaping dies of preferred use is described: because existing mold hot conductivity height, so even molten resin contacts with mould, the temperature of mould also is difficult to rise, thereby be difficult to reach the lower boiling volatile matter temperature province that discharges takes place to decompose, if but use the heat insulating ability shaping dies, then because thermal conductivity low, so die temperature raise easily, thereby reach suitable blowing temperature zone easily.Though use heat insulating mold can have the cooling performance downward trend, can not drop to the practical degree that goes up the generation problem.

In shaping dies, carry out active energy ray irradiation and temperature simultaneously and pressure controlled method is: in shaping dies, use silica glass, from the circumfusion active energy ray of shaping dies, and the control of heating and pressurizeing.In addition, also have following method etc.: silica glass is installed on the part of cylinder of injection forming, the resin irradiation active energy ray from the cylinder outside in cylinder carries out injection forming in shaping dies, foams simultaneously and is shaped.

Can suitably adopt the moulding method of the cited mistake in front in the operation of foamed process postforming foams, but compare, preferably the shaping of foaming simultaneously with the shaping behind the foamed process.Because can not destroy the foamy structure that specially forms, and the interior pressure that can utilize foaming to produce improves the transfer efficiency of shaping dies face.

In forming process, can obtain to have the foams of two-layer at least above laminar structure by laminating molding.Laminated each layer can be foaming layer, also can be nonfoamed layer.In order to obtain the foams of bubble distribution random variation, can utilize laminating molding.Be set at the transformable body irradiation active energy ray that is laminated into to concentration distribution, make its foaming by carrying out pressure-controlling in the temperature province that decomposition release takes place at the lower boiling volatile matter, thereby can be made into foams foaming composition.Changed being laminated in the body of concentration distribution of foaming composition, that can enumerate has: laminate, foaming composition and the non-foaming composition of the layer that the decomposability compound is different with the mixture ratio of light acid producing agent (or alkali generation agent) layer laminate etc.

Below, foaminess composition of the present invention is described.Foaming composition is to implement the composition that heat treated shows foaminess by the irradiation active energy ray.As this foaminess composition, the composition of preferred following at least two kinds of constituents coexistence.The first is utilized the effect of active energy ray and acidic acid producing agent or the alkali that produces alkali produce agent, and another kind is that the lower boiling volatile compound that acid or the alkali reaction with above-mentioned generation makes more than one decomposes the reducing foaming property compound that discharges.

Acid producing agent and alkali produce agent

Employed acid producing agent of foaminess composition that uses among the present invention or alkali produce agent, can use to be applied to material in chemical amplification photo etching glue and the light cationoid polymerisation etc., that be called as light acid producing agent or light alkali generation agent.

Can enumerate as suitable smooth acid producing agent of the present invention and to be selected from

(1) diazonium salt series compound

(2) ammonium salt series compound

(3) salt compounded of iodine series compound

(4) sulfonium salt series compound

(5) oxonium salt series compound

(6) phosphonium salt series compounds

Deng in aromatic series or the PF of fatty compounds ₆-, AsF ₆-, SbF ₆-, CF ₃SO ₃-salt etc.Be listed below as its object lesson, but be not limited to these examples.

Enumerated:

Two (benzenesulfonyl) diazomethane,

Two (cyclohexyl alkylsulfonyl) diazomethane,

Two (tertiary butyl alkylsulfonyl) diazomethane,

Two (to the Methyl benzenesulfonyl base) diazomethane,

Two (4-chlorobenzene alkylsulfonyl) diazomethane,

Two (p-toluenesulfonyl) diazomethane,

Two (4-tert.-butylbenzene alkylsulfonyl) diazomethane,

Two (2,4-dimethylbenzene alkylsulfonyl) diazomethane,

Two (cyclohexyl alkylsulfonyl) diazomethane,

Benzoyl-benzenesulfonyl diazomethane,

Trifluoro-methanyl sulfonate,

The trifluoromethayl sulfonic acid trimethylsulfonium,

The trifluoromethayl sulfonic acid triphenylsulfonium,

The hexafluoro-antimonic acid triphenylsulfonium,

Trifluoromethayl sulfonic acid 2,4,6-trimethylphenyl-phenylbenzene sulfonium,

Trifluoromethayl sulfonic acid p-methylphenyl phenylbenzene sulfonium,

Phosphofluoric acid 4-phenyl thiophenyl phenylbenzene sulfonium,

Hexafluoro-antimonic acid 4-phenyl thiophenyl phenylbenzene sulfonium,

Hexafluoro-antimonic acid 1-(2-naphthoyl) sulfosalt,

Trifluoromethayl sulfonic acid 1-(2-naphthoyl) sulfosalt,

Hexafluoro-antimonic acid 4-hydroxyl-1-naphthyl dimethyl sulfonium,

Trifluoromethayl sulfonic acid 4-hydroxyl-1-naphthyl dimethyl sulfonium,

Trifluoromethayl sulfonic acid (2-Oxy-1-cyclohexyl) (cyclohexyl) methyl sulfonium,

Trifluoromethayl sulfonic acid (2-Oxy-1-cyclohexyl) (2-bornyl) methyl sulfonium,

Perfluoromethane sulfonic acid phenylbenzene-4-aminomethyl phenyl sulfonium,

Perfluorooctane sulfonates phenylbenzene-4-tert-butyl-phenyl sulfonium,

Perfluorinated butane sulfonic acid phenylbenzene-4-p-methoxy-phenyl sulfonium,

Toluenesulphonic acids phenylbenzene-4-aminomethyl phenyl sulfonium,

Toluenesulphonic acids phenylbenzene-4-p-methoxy-phenyl sulfonium,

Toluenesulphonic acids phenylbenzene-4-isopropyl phenyl sulfonium,

Phenylbenzene iodine,

The toluenesulphonic acids diphenyl iodnium,

Phenylbenzene iodine muriate,

The hexafluoroarsenate diphenyl iodnium,

The phosphofluoric acid diphenyl iodnium,

The nitric acid diphenyl iodnium,

The perchloric acid diphenyl iodnium,

The trifluoromethayl sulfonic acid diphenyl iodnium,

Two (aminomethyl phenyl) salt compounded of iodine of trifluoromethayl sulfonic acid,

Two (aminomethyl phenyl) salt compounded of iodine of Tetrafluoroboric acid,

Two (aminomethyl phenyl) salt compounded of iodine of phosphofluoric acid,

Two (aminomethyl phenyl) salt compounded of iodine of hexafluoro-antimonic acid,

Two (4-tert-butyl-phenyl) salt compounded of iodine of trifluoromethayl sulfonic acid,

Two (4-tert-butyl-phenyl) salt compounded of iodine of phosphofluoric acid,

Two (4-tert-butyl-phenyl) salt compounded of iodine of hexafluoro-antimonic acid,

Two (4-tert-butyl-phenyl) salt compounded of iodine of perfluorinated butane sulfonic acid,

2-methyl-4,6-two (trichloromethyl)-1,3,5-triazines,

2,4,6-three (trichloromethyl)-1,3,5-triazines,

2-phenyl-4,6-two trichloromethyls-1,3,5-triazines,

2-(p-methoxyphenyl)-4,6-two trichloromethyls-1,3,5-triazines,

2-naphthyl-4,6-two trichloromethyls-1,3,5-triazines,

2-naphthyl-4,6-two trichloromethyls-1,3,5-triazines,

2-biphenyl-4,6-two trichloromethyls-1,3,5-triazines,

2-(4 '-hydroxyl-4-biphenyl)-4,6-two trichloromethyls-1,3,5-triazines,

2-(4 '-methyl-4-biphenyl)-4,6-two trichloromethyls-1,3,5-triazines,

2-(p-methoxyphenyl vinyl)-4,6-two (trichloromethyl)-1,3,5-triazines,

2-(4-chloro-phenyl-)-4,6-two (trichloromethyl)-1,3,5-triazines,

2-(4-p-methoxy-phenyl)-4,6-two (trichloromethyl)-1,3,5-triazines,

2-(4-methoxyl group-1-naphthyl)-4,6-two (trichloromethyl)-1,3,5-triazines,

2-(benzene [d] [1,3] dioxolane-5-yl)-4,6-two (trichloromethyl)-1,3,5-triazines,

2-(4-methoxyl-styrene)-4,6-two (trichloromethyl)-1,3,5-triazines,

2-(3,4,5-trimethoxy styryl)-4,6-two (trichloromethyl)-1,3,5-triazines,

2-(3, the 4-dimethoxy-styryl)-4,6-two (trichloromethyl)-1,3,5-triazines,

2-(2, the 4-dimethoxy-styryl)-4,6-two (trichloromethyl)-1,3,5-triazines,

2-(2-methoxyl-styrene)-4,6-two (trichloromethyl)-1,3,5-triazines,

2-(4-butyl phenyl ether vinyl)-4,6-two (trichloromethyl)-1,3,5-triazines,

2-(4-amyl phenyl ether vinyl)-4,6-two (trichloromethyl)-1,3,5-triazines,

Trifluoromethayl sulfonic acid 2,6-two-tertiary butyl-4-methyl pyrans,

Tetrafluoroboric acid trimethylammonium oxonium salt,

Tetrafluoroboric acid triethyl oxonium salt,

Trifluoromethayl sulfonic acid N-hydroxyphthalimide,

Trifluoromethayl sulfonic acid N-hydroxyl naphthalimide,

(α-benzoyl benzil) tosilate,

(β-benzoyl-beta-hydroxyphenyl ethyl) tosilate,

1,2, the basic trifluoro-methanyl sulfonate of 3-phenyl-three,

(2,6-dinitrobenzene benzil) tosilate,

(2-nitro benzil) tosilate,

(4-nitro benzil) tosilate etc.Wherein, preferred salt compounded of iodine series compound, sulfonium salt series compound.

In addition, except that described compound, also can use: the sulfonated bodies of induced generation sulfonic acid, for example 2-benzene sulfonyl phenyl methyl ketone by the irradiation active energy ray; By irradiation active energy ray and the halogenide of induced generation hydrogen halide, phenyl trisbromomethyl sulfone and 1 for example, 1-two (4-chloro-phenyl-)-2,2,2-trichloroethane; And by active energy ray irradiation and the ferrocene-containing compound of induced generation phosphoric acid, for example two (cyclopentadienyl) ferrocene salts of phosphofluoric acid, two (benzil) ferrocene salts of phosphofluoric acid etc.

In addition, also can use the imide compound derivative of enumerating below with acidic ability.

Enumerated:

N-(phenylsulfonyloxy) succinimide,

N-(trifluoromethyl sulfonyloxy) succinimide,

N-(10-camphor sulfonyloxy) succinimide,

N-(trifluoromethyl sulfonyloxy) phthalic imidine,

N-(trifluoromethyl sulfonyloxy)-5-norbornylene-2, the 3-dicarboximide,

N-(trifluoromethyl sulfonyloxy)-5-norbornylene-2, the 3-naphthalimide,

N-(10-camphor sulfonyloxy) naphthalimide.

Enumerated as being fit to smooth alkali generation agent of the present invention:

(1) oxime ester series compound

(2) ammonium series compound

(3) bitter almond oil camphor series compound

(4) benzil of dimethoxy urethane series compound

(5) ortho-nitrophenyl idol acyl urethane series compound etc., these materials produce amine as alkali by the irradiation active energy ray.In addition, also can use the alkali that utilizes light action to produce ammonia, hydroxyl ion to produce agent.These materials for example can be selected from N-(2-oil of mirbane idol acyloxy phosphinylidyne) hexahydropyridine, 1,3-two (N-(2-oil of mirbane idol acyloxy phosphinylidyne)-4-hexahydropyridine) propane, N, N '-two (2-oil of mirbane idol acyloxy phosphinylidyne) dihexylamine, adjacent benzil phosphinylidyne-N-(1-phenyl ethylidene) azanol etc.In addition, also can will produce agent and usefulness by compound and the above-mentioned smooth alkali that adds thermogenesis alkali.

In addition, in order to enlarge the wavelength region may that light acid producing agent or light alkali produce the active energy ray of agent, also can suitably and use photosensitizers.For example, the photosensitizers of salt compound has been enumerated trypaflavine, benzene flavine, acridine orange etc. relatively.

As when generating necessary acid, also addition and the rayed energy with acid producing agent or alkali generation agent is controlled to be minimal method, can be with acid proliferation generator, alkali multiplication agent (K.Ichimuraetal., Chemistry Letters, 551-552 (1995), Japanese patent laid-open 8-248561 communique, Japanese Patent spy open the 2000-330270 communique) use with acid producing agent or alkali generation agent.Acid proliferation generator is in the Thermodynamically stable state under near the normal temperature, but the theobromine decomposition, self produces strong acid, can significantly accelerate the acid catalyst reaction.Utilize this reaction, can improve the generation efficient of acid or alkali, also may command foam formation speed and foamy structure.

Reducing foaming property compound:

Employed the reducing foaming property compound of the foaminess composition that uses among the present invention (being designated hereinafter simply as the decomposability compound) can with acid or alkali reaction, decompose, discharge more than one lower boiling volatile matter (lower boiling volatile compound).That is, in this decomposability compound, must import the decomposability functional group that can produce the lower boiling volatile matter in advance.Gasification temperature reached the upper limit when so-called lower boiling was meant foaming.The boiling point of low-boiling compound is generally below 100 ℃, is preferably below the normal temperature.As having that the lower boiling volatile matter can be enumerated: for example iso-butylene (boiling point-7 ℃), carbonic acid gas (boiling point-79 ℃), nitrogen (boiling point-196 ℃) etc.As decomposability functional group, can enumerate the tertiary butyl, tertiary butyl oxygen carbonyl, ketone acid and ketone acid ester group etc. with the group of acid-respons, can enumerate polyurethane-base, carbonate based etc. with the group of alkali reaction.As with the functional group of acid-respons, the tertiary butyl, tertiary butyl oxygen carbonyl and acid react, and the tertiary butyl generates isobutene gas, and tertiary butyl oxygen carbonyl generates isobutene gas and carbonic acid gas, and ketone acid partly generates carbonic acid gas, and the keto ester for example ketone acid tertiary butyl generates carbonic acid gas and iso-butylene.As with the decomposability functional group of alkali reaction, polyurethane-base, carbonate based generate carbon dioxide.Like this, all gases discharges from the decomposability compound.Example as acid (or alkali) decomposition compound can use monomer, oligopolymer, macromolecular compound (polymkeric substance) etc., for example can be categorized as following compound group.

(1) the decomposability compound group of the low molecular series of non-solidified nature

(2) the decomposability compound group of solidified nature series monomer

(3) the decomposability compound group of series of polymers

Typical case as the decomposability compound of solidified nature series monomer, when adopting at the irradiation active energy ray polymerization reaction take place contain the active energy ray-curable compound of vinyl the time, form uniform micro bubble easily, can obtain the higher foams of intensity.The object lesson of decomposability compound is listed below, but is not limited to these examples.

That can enumerate has:

(1)-the decomposability compound group of the low molecular series of a, non-solidified nature

＜sour decomposability compound 〉

1-tert.-butoxy-2-Ethoxyethane,

2-(tert butoxy carbonyl oxygen base) naphthalene,

N-(tert butoxy carbonyl oxygen base) phthalic imidine,

2,2-two [to (tert butoxy carbonyl oxygen base) phenyl] propane etc.

(1)-the decomposability compound group of the low molecular series of b, non-solidified nature

＜alkali decomposability compound 〉

N-(9-fluorenyl methoxy phosphinylidyne) hexahydropyridine etc.

(2)-the decomposability compound group of a, solidified nature series monomer

＜sour decomposability compound 〉

Tert-butyl acrylate,

The methacrylic tert-butyl acrylate,

Vinylformic acid tert butoxy carbonyl methyl esters,

Vinylformic acid-2-(tert butoxy carbonyl) ethyl ester,

Vinylformic acid to (tert butoxy carbonyl) phenyl ester,

Vinylformic acid to (tert butoxy carbonyl ethyl) phenyl ester,

Vinylformic acid-1-(tert butoxy carbonyl methyl) cyclohexyl,

Vinylformic acid-4-tert butoxy carbonyl-8-vinyl carbon acyloxy-trichlorine [5.2.1.02,6] decane,

Vinylformic acid-2-(tert butoxy carbonyl oxygen base) ethyl ester,

Vinylformic acid to (tert butoxy carbonyl oxygen base) phenyl ester,

Vinylformic acid to (tert butoxy carbonyl oxygen base) benzyl ester,

Vinylformic acid-2-(tert butoxy carbonyl amino) ethyl ester,

The own ester of vinylformic acid-6-(tert butoxy carbonyl amino),

Vinylformic acid to (tert butoxy carbonyl amino) phenyl ester,

Vinylformic acid to (tert butoxy carbonyl amino) benzyl ester,

Vinylformic acid to (tert butoxy carbonyl amino methyl) benzyl ester,

(2-tert.-butoxy ethyl) acrylate,

(3-tert.-butoxy propyl group) acrylate,

Vinylformic acid-(1-tertiary butyl dioxy base-1-methyl) ethyl ester,

Vinylformic acid-3,3-two (tertiary butyl oxygen base phosphinylidyne) propyl ester,

Vinylformic acid-4,4-two (tertiary butyl oxygen base phosphinylidyne) butyl ester,

To (tert.-butoxy) vinylbenzene,

Between (tert.-butoxy) vinylbenzene,

To (tert butoxy carbonyl oxygen base) vinylbenzene,

Between (tert butoxy carbonyl oxygen base) vinylbenzene,

Acryloyl acetic acid, methacryloyl acetic acid,

Tertiary butyl acryloyl acetic acid,

Tertiary butyl methacryloyl acetic acid,

N-(tert butoxy carbonyl oxygen base) maleimide

(2)-the decomposability compound group of b, solidified nature series monomer

＜alkali decomposability compound 〉

4-[(1,1-dimethyl-2-cyano group) oxyethyl group carbon acyloxy] vinylbenzene,

4-[(1,1-dimethyl-2-benzene sulfonyl) oxyethyl group carbon acyloxy] vinylbenzene,

4-[(1,1-dimethyl-2-methoxyl group sulphonyl) oxyethyl group carbon acyloxy] vinylbenzene,

4-(2-cyano group oxyethyl group carbon acyloxy) vinylbenzene,

Methacrylic acid-(1,1-dimethyl-2-benzene sulfonyl) ethyl ester,

Methacrylic acid-(1,1-dimethyl-2-cyano group) ethyl ester etc.

(3)-the decomposability compound group of a, series of polymers

＜sour decomposability compound 〉

Poly-(tert-butyl acrylate),

Poly-(methacrylic tert-butyl acrylate),

Poly-(vinylformic acid tert butoxy carbonyl methyl esters),

Poly-[vinylformic acid-2-(tert butoxy carbonyl) ethyl ester],

Poly-[vinylformic acid is to (tert butoxy carbonyl) phenyl ester],

Poly-[vinylformic acid is to (tert butoxy carbonyl ethyl) phenyl ester],

Poly-[vinylformic acid-1-(tert butoxy carbonyl methyl) cyclohexyl],

Poly-[vinylformic acid-4-tert butoxy carbonyl-8-vinyl carbon acyloxy-trichlorine [5.2.1.02,6] decane],

Poly-[vinylformic acid-2-(tert butoxy carbonyl oxygen base) ethyl ester],

Poly-[vinylformic acid is to (tert butoxy carbonyl oxygen base) phenyl ester],

Poly-[vinylformic acid is to (tert butoxy carbonyl oxygen base) benzyl ester],

Poly-[vinylformic acid-2-(tert butoxy carbonyl amino) ethyl ester],

Poly-[the own ester of vinylformic acid-6-(tert butoxy carbonyl amino)],

Poly-[vinylformic acid is to (tert butoxy carbonyl amino) phenyl ester],

Poly-[vinylformic acid is to (tert butoxy carbonyl amino) benzyl ester],

Poly-[vinylformic acid is to (tert butoxy carbonyl amino methyl) benzyl ester],

Poly-(vinylformic acid-2-tert.-butoxy ethyl ester),

Poly-(vinylformic acid-3-tert.-butoxy propyl ester),

Poly-[vinylformic acid-(1-tertiary butyl dioxy base-1-methyl) ethyl ester],

Poly-[vinylformic acid-3,3-two (tertiary butyl oxygen base phosphinylidyne) propyl ester],

Poly-[vinylformic acid-4,4-two (tertiary butyl oxygen base phosphinylidyne) butyl ester],

Poly-[to (tert.-butoxy) vinylbenzene],

Poly-[(tert.-butoxy) vinylbenzene],

Poly-[to (tert butoxy carbonyl oxygen base) vinylbenzene],

Poly-[(tert butoxy carbonyl oxygen base) vinylbenzene],

Polyacrylamide acetic acid, polymethyl acyl acetic acid,

Poly-[tertiary butyl acryloyl acetic acid],

Poly-[tertiary butyl methacryloyl acetic acid],

N-(tert butoxy carbonyl oxygen base) maleimide/styrol copolymer

(3)-the decomposability compound group of b, series of polymers

＜alkali decomposability compound 〉

Poly-{ to [(1,1-dimethyl-2-cyano group) oxyethyl group carbon acyloxy] vinylbenzene },

Poly-{ to [(1,1-dimethyl-2-benzene sulfonyl) oxyethyl group carbon acyloxy] vinylbenzene },

Poly-{ to [(1,1-dimethyl-2-methoxyl group sulphonyl) oxyethyl group carbon acyloxy] vinylbenzene },

Poly-[to (2-cyano group oxyethyl group carbon acyloxy) vinylbenzene],

Poly-[methacrylic acid-(1,1-dimethyl-2-benzene sulfonyl) ethyl ester],

Poly-[methacrylic acid-(1,1-dimethyl-2-cyano group) ethyl ester] etc.

Importing can there be the organic series macromolecular compounds such as polyethers, polymeric amide, polyester, polyimide, polyvinyl alcohol, dendritic crystal of decomposability functional group to use as sour decomposability or alkali decomposability series of polymers compound.In addition, also comprise sour decomposability or the alkali decomposability series of polymers compound that in inorganic series compounds such as silicon-dioxide, imports decomposability functional group.Wherein, decomposability functional group preferably imports in the compound group with the functional group that is selected from carboxylic acid group or hydroxyl, amido.

Above-mentioned decomposability compound can use separately, also can will use simultaneously after the different two or more mixing.In addition, above-mentioned decomposability compound also can with other mixed with resin after re-use.During mixing, decomposability compound and other resins can mix also can be immiscible.Can from following normally used resin, suitably select to use as other resins: polyethylene terephthalate, vibrin such as polybutylene terephthalate, unsaturated polyester resin, polycarbonate resin, polyethylene, polyolefin series resins such as polypropylene, polyolefin series compound resin, polystyrene resin, polybutadiene, (methyl) acrylic resin, acryloyl resin, ABS resin, fluoro-resin, polyimide resin, polyacetal resin, polysulfone resin, vinyl chloride resin, methylcellulose gum, ethyl cellulose, hydroxypropylcellulose, starch, polyvinyl alcohol, polyamide resin, phenolic resin, melamine resin, urea resin, urethane resin, Resins, epoxy and silicone resin etc.In addition, be present in the molding, also can use gas barrier resins in order to make the lower boiling volatile matter that from the decomposability compound, decomposes the back gasification.Gas barrier resins can mix, and also can coat, also can lamination, be present in the molding in order to make the lower boiling volatile matter better, and preferably coat or be laminated on the molding surface.

In decomposability foaming compound, can use the decomposability compound group of solidified nature series monomer and the decomposability compound group of series of polymers separately, also can use with above-mentioned normally used mixed with resin.Relative therewith, the decomposability compound group of the low molecular series of non-solidified nature can not be shaped separately, so must use with above-mentioned normally used mixed with resin.

In order to improve the water-repellancy of foams of the present invention, also can use the compound that imports reducing foaming property functional group to the compound that contains the hydrophobic functional groups more than at least a as the foaminess composition.The hydrophobic functional groups of using among the present invention mainly is selected from fatty group, alicyclic group, aromatic series base, halogen radical, itrile group.Reducing foaming property functional group is directed among the hydrophilic functional group who mainly is selected from carboxylic acid group or hydroxyl, amido easily.Therefore, as decomposability compound of the present invention, preferably by importing the decomposability unit of reducing foaming property functional group to described hydrophilic functional group and containing the complex chemical compound that the hydrophobic unit of hydrophobic functional groups constitutes.More preferably, the decomposability unit of described complex chemical compound and hydrophobic unit are the ethene series polymers.What hydrophobic unit can be enumerated has: aliphatics (methyl) acrylate such as (methyl) methyl acrylate, (methyl) ethyl propenoate, aromatic ethylene compounds such as vinylbenzene, vinyl toluene, vinylnaphthalene, the group of (methyl) acrylonitrile compound, the vinyl acetate between to for plastic compound, and the vinylchlorid compound etc.Exemplary as the decomposability compound, can enumerate the ethene series copolymer that constitutes by decomposability unit and hydrophobic unit, wherein, the decomposability unit is to be that carboxylic acid group's vinylformic acid imports that decomposability functional group is arranged is the tert-butyl acrylate of the tertiary butyl to possess hydrophilic property functional group, and hydrophobic unit is to have the methyl acrylate that hydrophobic functional groups is a methyl.The object lesson of the decomposability compound that is constituted by decomposability unit/hydrophobic unit is as follows:

Tert-butyl acrylate/methylmethacrylate copolymer,

Methacrylic tert-butyl acrylate/methyl acrylate copolymer,

Methacrylic tert-butyl acrylate/methylmethacrylate copolymer,

Tert-butyl acrylate/ethyl acrylate copolymer,

Tert-butyl acrylate/ethyl methacrylate copolymers,

Methacrylic tert-butyl acrylate/ethyl acrylate copolymer,

Methacrylic tert-butyl acrylate/ethyl methacrylate copolymers,

Tert-butyl acrylate/styrol copolymer,

Tert-butyl acrylate/vinyl chloride copolymer,

Tert-butyl acrylate/acrylonitrile copolymer,

To (tert butoxy carbonyl oxygen base) vinylbenzene/styrol copolymer

In addition, decomposability unit and hydrophobic unit in the decomposability compound can be used alone, and also can use two or more simultaneously.The form of copolymerization can at random adopt random copolymerization, block copolymerization, graft copolymerization etc.In addition, preferred 5～95 quality % of the relative decomposability total amount of compound of the copolymerization ratio of hydrophobic unit consider the environment keeping quality of the reducing foaming property and the foamy structure of decomposability compound, more preferably 20～80 quality %.

Above-mentioned decomposability compound can use separately, also can will use simultaneously after the different two or more mixing.Thereby above-mentioned decomposability compound reducing foaming property functional group decompose to discharge produce be used to form the gas of bubble after, become the compound that contains at least a above hydrophobic functional groups.

In order to improve the water-repellancy of foams of the present invention, also can use the compound that in the agent of low hygroscopicity compound, imports reducing foaming property functional group as the foaminess composition, wherein, this agent of low hygroscopicity compound is that 30 ℃, relative humidity are that the equilibrium water absorption measured with the JISK7209D method under 60% the environment is less than 10% in temperature.As the agent of low hygroscopicity compound with the structure that is easy to import reducing foaming property functional group, that can enumerate has: for example, and para hydroxybenzene ethene, a hydroxy styrenes etc.What therefore, the decomposability compound can be enumerated has: to tert.-butoxy vinylbenzene, a tert.-butoxy vinylbenzene, to tert butoxy carbonyl oxygen base vinylbenzene, a tert butoxy carbonyl oxygen base vinylbenzene.These materials can be the solidified nature monomer, also can be for mixing more than one polymer of monomers.

In addition, also can in the complex chemical compound that to be high-hygroscopicity compound more than 10% and water-intake rate by water-intake rate constitute less than 10% agent of low hygroscopicity compound, import reducing foaming property functional group.But complex chemical compound preferably has the water-intake rate less than 10% after by appropriate combination.For example, as the vinylformic acid of high-hygroscopicity compound with as the multipolymer (complex chemical compound) of the para hydroxybenzene ethene of agent of low hygroscopicity compound, preferably its copolymerization ratio is vinylformic acid/para hydroxybenzene ethene=90/10～0/100.Object lesson as the decomposability compound has:

Tert-butyl acrylate/to the tert.-butoxy styrol copolymer,

A tert-butyl acrylate/tert.-butoxy styrol copolymer,

Tert-butyl acrylate/to tert butoxy carbonyl oxygen base styrol copolymer,

A tert-butyl acrylate/tert butoxy carbonyl oxygen base styrol copolymer,

The methacrylic tert-butyl acrylate/to tert butoxy carbonyl oxygen base styrol copolymer.

In addition, also can be to reducing foaming property of the importing functional groups such as agent of low hygroscopicity macromolecular material in being selected from the combination of forming by polyester, polyimide, Vinyl Acetate Copolymer, polyvinyl chloride, polyacrylonitrile, phenolic resin, dendritic crystal.

Above-mentioned decomposability compound can use separately, also can will use simultaneously after the different two or more mixing.Above-mentioned decomposability compound forms the agent of low hygroscopicity compound after thereby the decomposition release generation of reducing foaming property functional group is used to form the gas of bubble.

The foaminess composition:

The foaminess composition deacidification of using among the present invention produces agent or alkali produces outside agent and the reducing foaming property compound, also can be used in combination other active energy ray-curable unsaturated organic compound.With the example of compound, specifiable have as also:

(1) (methyl) esters of acrylic acid of the alcohols of aliphatics, alicyclic, aromatic 1～6 valency and poly-alkyl ethylene glycol

(2) in the alcohols of aliphatics, alicyclic, aromatic 1～6 valency, add alkylene oxide and (methyl) esters of acrylic acid of the compound that obtains

(3) poly-(methyl) acryloyl alkyl phosphate class

(4) polyprotonic acid, polyol and (methyl) acrylic acid resultant of reaction

(5) isocyanic ester, polyol, (methyl) acrylic acid resultant of reaction

(6) epoxy compounds and (methyl) acrylic acid resultant of reaction

(7) epoxy compounds, polyol, (methyl) acrylic acid resultant of reaction

(8) trimeric cyanamide and (methyl) acrylic acid resultant of reaction etc.

Can and the compound of usefulness in, solidified nature monomer and resin can play the such rerum natura of the intensity that improves foams and thermotolerance and the effect of control foaminess etc.In addition, when the decomposability compound and and with compound in during use solidified nature monomer, a kind of manufacture method that solvent can be shaped and carrying capacity of environment is little of not using can be provided.For example, just used this material in the Japanese patent laid-open 9-102230 communique.

As also having: methyl acrylate with the object lesson of compound is specifiable, ethyl propenoate, dodecyl acrylate, octadecyl acrylate, ethyl acrylate, 2-Hydroxy ethyl acrylate, methacrylic acid-2-hydroxy methacrylate, vinylformic acid-2-hydroxy propyl ester, methacrylic acid-2-hydroxy propyl ester, vinylformic acid-2-hydroxyl butyl ester, methacrylic acid-2-hydroxyl butyl ester, the vinylformic acid tetrahydro furfuryl ester, the methacrylic acid tetrahydro furfuryl ester, caprolactone modification vinylformic acid tetrahydro furfuryl ester, cyclohexyl acrylate, cyclohexyl methacrylate, vinylformic acid two cyclohexyls, isobornyl acrylate, isobornyl methacrylate, benzyl acrylate, benzyl methacrylate, oxyethyl group Diethylene Glycol acrylate, methoxyl group triethylene glycol acrylate, the MPEG acrylate, the phenoxy group polyethylene glycol acrylate, phenoxy group polypropylene glycol acrylate, oxyethane modification phenoxy group acrylate, vinylformic acid-N, the N-dimethylamino ethyl ester, methacrylic acid-N, the N-dimethylamino ethyl ester, 2-ethylhexyl Trivalin SF acrylate, ω-carboxyl polycaprolactone single-acrylate, phthalandione monohydroxy ethyl propylene acid esters, acrylic acid dimer, 2-hydroxyl-3-phenoxy propyl acrylate, vinylformic acid-9,10-epoxidation oleoyl, the toxilic acid diethylene glycol monoacrylate, two cyclopentenes ethoxy ethylene base acrylate, 4,4-dimethyl-1, the accrete acrylate of the caprolactone of 3-dioxolane, 3-methyl-5,5-dimethyl-1, the accrete acrylate of the caprolactone of 3-dioxolane, the PBAA ester, oxyethane modification phenoxy group p thiodipropionic acid ester, glycol diacrylate, ethylene glycol dimethacrylate, 1, the ammediol diacrylate, 1, the ammediol dimethacrylate, 1, the 4-butylene glycol diacrylate, 1, the 4-butylene glycol dimethacrylate, 1, the 6-hexanediyl ester, 1, the 6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate, diethylene glycol diacrylate, polyethyleneglycol diacrylate, polyethylene glycol dimethacrylate, polypropyleneglycol diacrylate, polypropylene glycol dimethacrylate, neopentylglycol diacrylate, 2-butyl-2-ethyl glycol diacrylate, dihydroxyphenyl propane-oxyethane modification diacrylate, dihydroxyphenyl propane-polyethylene oxide modification diacrylate, Hydrogenated Bisphenol A-polyethylene oxide modification diacrylate, dihydroxyphenyl propane-epoxy pronane modification diacrylate, dihydroxyphenyl propane-poly(propylene oxide) modification diacrylate, isocyanuric acid oxyethane modification diacrylate, tetramethylolmethane diacrylate monoesters, 1,6-hexanediol diglycidyl ether vinylformic acid annexation, dihydroxyphenyl propane-polyoxyethylene Epicholorohydrin modification diacrylate, Viscoat 295, TriMethylolPropane(TMP) oxyethane modification triacrylate, TriMethylolPropane(TMP) polyethylene oxide modification triacrylate, TriMethylolPropane(TMP) epoxy pronane modification triacrylate, TriMethylolPropane(TMP) poly(propylene oxide) modification triacrylate, pentaerythritol triacrylate, isocyanuric acid oxyethane modification triacrylate, glycerol oxyethane modification triacrylate, glycerol polyethylene oxide modification triacrylate, glycerol epoxy pronane modification triacrylate, glycerol poly(propylene oxide) modification triacrylate, tetramethylol methane tetraacrylate, two (TriMethylolPropane(TMP)) tetraacrylate, the Dipentaerythritol tetraacrylate, Dipentaerythritol five acrylate, dipentaerythritol acrylate, Dipentaerythritol caprolactone modification six acrylate, Dipentaerythritol polycaprolactone modification six acrylate etc., but be not limited to these.

In addition, as above-mentioned and with part or all of active energy ray-curable unsaturated organic compound, can be about 400～5000 active energy ray-curable resin combination also with have (methyl) acryl and molecular weight at molecule chain end.Preferably use for example polyurethane-modified polyethers to gather polyurethane polyureas (methyl) the acrylic ester polymer class of (methyl) acrylate, poly-(methyl) acrylate of polyurethane-modified polyester etc. as this curable resin.

The foaminess composition that uses among the present invention also can contain the additive beyond the decomposability compound as required.As additive, can contain in the following material more than one: inorganic or organic filler, and dispersion agent such as various tensio-active agents, polyvalent isocyanate compound, epoxy compounds, organometallic compound isoreactivity compound and antioxidant, silicone oil and processing aid, UV light absorber, white dyes, slipproofing agent, anti-electrostatic agent interfering, anticaking agent, preventing clouding agent, photostabilizer, slipping agent, tenderizer, coloured dyestuff, other stablizers etc.By using additive, can expect to improve plasticity and foaminess, optics rerum natura (the especially situation of white pigment), electric and magnetism characteristic (the especially situation of electroconductive particle such as carbon) etc.

Object lesson as inorganic series compound weighting agent, that can enumerate has: pigment such as titanium oxide, magnesium oxide, aluminum oxide, silicon oxide, lime carbonate, barium sulfate, magnesiumcarbonate, Calucium Silicate powder, aluminium hydroxide, clay, talcum, silica, the metallic soap as Zinic stearas, and dispersion agent such as various tensio-active agents, calcium sulfate, sal epsom, kaolin, silicic acid carclazyte, diatomite, zinc oxide, silicon oxide, magnesium hydroxide, calcium oxide, magnesium oxide, alumina, mica, asbestos powder, glass powder, volcanic ash (シ ラ ス バ Le one Application), zeolite etc.As organic series compound weighting agent, that can enumerate has: Mierocrystalline cellulose such as timber powder, paper pulp powder series powder for example.

As organic series compound weighting agent, that can enumerate has: for example Mierocrystalline cellulose such as timber powder, paper pulp powder series powder, and polymer beads etc.As polymer beads, for example can use: the material of making by acrylic resin, styrene resin or derivatived cellulose, polyvinyl resin, polyvinyl chloride, polyester, urethane and polycarbonate and crosslinkable monomer etc.

These weighting agents can mix two or more.

As the object lesson of UV light absorber, can be selected from salicylic acid series, benzophenone series or benzotriazole series UV light absorber.As Whitfield's ointment is having of can enumerating of UV light absorber: salol, p-t-butylphenyl salicylate, p-octylphenyl salicylate etc.As benzophenone is UV light absorber, and that can enumerate has: 2, and 4-dihydroxy-benzene ketone, 2-hydroxyl-4-anisole ketone, 2-hydroxyl-4-octyloxy benzophenone, 2,2 '-dihydroxyl-4-anisole ketone etc.As benzotriazole is UV light absorber, and that can enumerate has: 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, 2-(2 '-5 '-tert-butyl-phenyl) benzotriazole etc.

As the object lesson of antioxidant, that can enumerate has: single phenol is, bis-phenol is, polymer phenol is antioxidant, and Sulfur is an antioxidant, and phosphorous antioxidant etc.

As the typical case of photostabilizer, can enumerate the hindered amine series compound.

Tenderizer can be used to improve the processibility of plasticity or molding, specifically can enumerate: ester series compound class, amide compound class, the hydrocarbon polymer class with side chain, mineral oils, whiteruss and wax class etc.

The monomer or the polyester of the structure that constitutes as ester cpds so long as by alcohols and carboxylic acid get final product, and do not have particular restriction, can be at the residual compound that hydroxyl and carbonic acyl radical end are arranged of intramolecularly, also can be the compounds with the form closure of ester group.That specifically can enumerate has: stearyl stearate, sorbitan stearate, epoxy soybean oil, refined caster oil, hardened castor oil, synourin oil, epoxy soybean oil, extreme winterized stearin, benzenetricarboxylic acid three monooctyl esters, ethylene glycol bisthioglycolate octylate and tetramethylolmethane four octylates etc.

The monomer or the polyamide compound of the structure that constitutes as amide compound so long as by amine and carboxylic acid get final product, and do not have particular restriction, can be at the residual compound that amino and carbonic acyl radical end are arranged of intramolecularly, also can be the compounds with the form closure of amide group.That specifically can enumerate has: the derivative of stearic amide, behenamide, the two stearic amides of hexamethylene, the two octyl group acid of trimethylene acid amides, the two oxystearic acid acid amides of hexamethylene, trioctylphosphine trihemellitic acid acid amides, two hard ester group urea, the two stearic amides of fourth support, the two stearic amides of xylylene, two hard ester group fatty acid amides, two hard ester group phthalic acid acid amides, two hard ester group octadecanoic acid acid amides, ε-Ji Neixianan and these materials.

As the hydrocarbon polymer with side chain, in the poly-alpha olefins class, preferably having carbonatoms is the material that is categorized as oligopolymer usually of the side chain more than 4.Specifically can enumerate: the multipolymer of ethylene-propylene and maleic acid derivatives thereof, the polymkeric substance of iso-butylene, the oligopolymer of divinyl, iso-butylene and hydride thereof, the polymkeric substance of 1-hexene, the polymkeric substance of polystyrene reaches by its deutero-derivative, hydroxyl polyhutadiene and hydride thereof, and the hydride of terminal polyhutadiene with hydroxyl etc.

The foaminess composition that uses among the present invention can use general mixing roll to modulate.For example: two rollers, three rollers, カ ウ レ ス デ ゾ Le バ one, homogeneous stirrer, sand mill, planetary stirring machine, ball mill, kneader (kneader), homogenizer, homogenizer etc.Also can use ultrasonic dispersing machine etc. in addition.

Foamy structure feature to the foams that obtain by manufacture method of the present invention describes below.It is more than the following 1 μ m of 10 μ m that the bubble distribution of the foams that obtained preferably is controlled at bubble diameter and number of bubbles density is 10 ⁹Individual/cm ³More than, more preferably 10 ¹¹Individual/cm ³In the above scope.As described in the application (Japanese patent application laid is willing to 2004-29107) before the inventor, the characteristic of the foams that obtained comprises the feature of all respects such as optical characteristics, thermal property, electrical specification.And the bubble of foams of the present invention distributes and can control arbitrarily with changing, so locate as the high functionality raw material with controllable foaming character distribution, is very useful.As foaming character, that for example can enumerate has: color developing, bulkiness, dry sensation, expansion sense, soft feel(ing), ventilation property, heat insulating ability, low electric capacity are forthright, scattering of light, light reflective, sheltering, white, opacity, to the reflection of wavelength selectivity and perviousness, light weight, floatability, sound insulation, sound absorbing, resiliency, damping property, absorptivity, adsorptivity, storage, perviousness, filterableness etc.These foams can be used for various uses, and can be used for for example wrapping material, medical material, electric installation material, electronic information material, automotive material etc.

＜inhomogeneous foams 〉

The foams that utilize the present invention to obtain be the distribution (being referred to as previously mentioned, " bubble distribution " sometimes) of bubble diameter and bubble density with the position different and different inhomogeneous foams.

(bubble diameter)

Bubble among the present invention directly is the meaning of bubble diameter.Particularly, be to obtain by asking for the mean value that carries out the bubble diameter that image analysis obtains from the observation image of foams section.In addition, in the visual field of profile image, extract the zone that to measure 100 above bubbles, averaged from its substantial middle near zone.

Bubble diameter is preferably in whole distribution range below the 10 μ m, is more preferably 0.005～10 μ m.When bubble diameter during less than 0.005 μ m, then the function on the foams is difficult to show.In addition, when bubble diameter during greater than 10 μ m, then the smoothness of foam surface may be abundant inadequately.Especially because thickness is the following slim foams of 100 μ m, the situation that bad order takes place is more, so preferred especially 0.005～1 μ m.

(bubble density)

Bubble density among the present invention can (contain bubble and be also contained in the interior density of interior per unit volume: g/cm by the volume density that is directly calculated by Archimedes's method ³) or expansion ratio (ratio of the volume density the when volume density when not foaming foams relatively: doubly), (the bubble number of volume is not individual/cm when foaming relatively for number of bubbles density ³) etc. the unit volume expression that converts estimate; It is (individual/cm also can to carry out bubble occupied area rate (%), number of bubbles area density that image analysis tries to achieve by the observation image from the foams section ²) etc. the unit surface expression that converts estimate.The bubble density of the inhomogeneous foams that obtain by the present invention is inequality according to the position difference in same foams, so, compare with the unit volume that adopts the Archimedes's method that needs a certain amount of even foams for the mensuration expression that converts, the unit surface that preferred employing can be measured by point from the profile image the expression that converts is estimated.

Bubble density obtains near this regional approximate centre the zone of measuring 100 above bubbles being taken a sample in the visual field of profile image.

The bubble density of foams of the present invention is not particularly limited, but in order fully to show the function of foams, with regard to number of bubbles density, is preferably 10 ⁹Individual/cm ³Above scope.Convert if this value is carried out unit surface, then for example when bubble diameter is 1 μ m, bubble occupied area rate is preferably more than 0.8%.

As the representative manner of bubble diameter or bubble density uneven distribution, can enumerate partial foaming and the foaming of tilting.

(partial foaming)

Partial foaming is exactly (1) and is divided into the mode of not foamed zones and foamed zones or is divided into the mode of hanging down foamed zones and high foamed zones.Even in the part foams, (2) not the mode of the mutual mode that exists of foamed zones and foamed zones or low foamed zones and the mutual existence of high foamed zones are also referred to as mutual foaming.Non-foamed zones Ia, Ic shown in Fig. 9 A, Ie and even foaming area I b, Id submit the mutual foams that interworking is put in part.Figure 10 A illustrates even foaming area I Ib, IIf that is formed by the small bubbles diameter and the mutual mutual foam that disposes of even foaming area I Id part between each non-foamed zones IIa, IIc, IIe, IIg that is formed by the air pocket diameter.In Fig. 9 A, Figure 10 A, M is the matrix of molding, and B is bubble (also to be identical in figure below).The foam of whichever figure among Fig. 9 A, Figure 10 A can change arbitrarily each regional width.

(foaming of tilting)

As the foaming of tilting, that can enumerate has: (3) in the zone of having foamed, bubble diameter or bubble density be (perhaps position) midway continually varying mode from one end to the other side; (4) in the zone of having foamed, bubble diameter or bubble density be the mode of (perhaps place) midway phasic Chang from one end to the other side.

State as phasic Chang, that can enumerate has: be divided into bubble distribute above zone of two different stages, the state of low foamed zones and high foamed zones for example, the perhaps state that changes along the order of low foamed zones, middle foamed zones, high foamed zones, the perhaps state that changes in the mode more than the four-stage.

Figure 11 A represents that bubble diameter is along same direction continually varying inclined foam.Figure 12 A represents that bubble density is along same direction continually varying inclined foam.

Under situation about distributing like this, trisection ground is divided into three zones on the continually varying direction, the mean air bubble diameter in the zone of bubble diameter or bubble density minimum is made as D1, average bubble occupied area rate is made as S1, the mean air bubble diameter in the middle zone of value of bubble diameter or bubble density is made as D2, average bubble occupied area rate is made as S2, the mean air bubble diameter in the zone of bubble diameter or bubble density maximum is made as D3, bubble occupied area rate is made as S3, this moment, the value of D3/D1 or S3/S1 was more than 1.01, be preferably more than 1.1, more preferably more than 1.2, especially be preferably more than 1.5.

So-called mean value is meant in the visual field of profile image the value of taking a sample near select to measure 100 above bubbles this regional approximate centre zone and measuring.

In addition, Figure 13 A represents that bubble diameter is along same direction (interim ground) inclined foam of changing discontinuously.In addition, Figure 14 A represents that bubble density is along same direction (interim ground) inclined foam of changing discontinuously.

Under the situation of this distribution, mean air bubble diameter D2 or average bubble occupied area rate S2 with the zone (Vc, VIc) of bubble diameter or bubble density maximum, when comparing with the mean air bubble diameter D1 in the zone (Va, VIa) of bubble diameter or bubble density minimum or average bubble occupied area rate S1, the value of D2/D1 or S2/S1 is more than 1.1, preferred more than 1.2, more preferably more than 1.5.So-called mean value is meant in visual the value of sampling near select to measure 100 above bubbles this regional approximate centre zone and measuring.

(other foaming modes)

As other foaming modes, can be listed below mode: at least one direction (x) that (5) bubble diameter (D) or bubble density (N) have in foams goes up continuous or discontinuously arranged distribution function D=F (x), N=F (x).

(5) foaming mode comprises the centre or the blended mode of (1) or (2) and (3) or (4) blended mode or (3) and (4).Perhaps, comprise and not foam or low foamed zones and high foamed zones completely random blended mode.

In above-mentioned example, though unqualified to the direction of bubble changes in distribution,, under the situation that is for example sheet foams, the preferred mode that changes along the in-plane of sheet or at least one direction in the thickness direction.

In addition, in Fig. 9～Figure 14, all be to number of bubbles and bubble density respectively the situation of independent variation be illustrated, but both change easily together usually, have such trend: when number of bubbles increased, bubble density also can increase; When number of bubbles reduced, bubble density also can reduce.

＜bubble skewness homogenize method 〉

Desired bubble distribute be by will be in following any one more than be set at that uneven distribution obtains: (a) be applied to the radioactive rays energy on the molding of preliminary forming operation shaping; (b) in the foams forming process, be applied to heat energy on the molding; (c) the reducing foaming property functional group concentration in the molding; (d) acid producing agent in the molding or alkali produce the concentration of agent.

If inhomogeneous foaming may size change on a part, so, need extruding in advance for molding can freely be out of shape.Go up in this respect, need to carry out pressure-controlling among the present invention, but, when bubble diameter is big, do not need to apply too big pressure, so long as (0.1～10MPa) gets final product slightly greatly with the normal atmosphere same degree or than it in order to obtain inhomogeneous foaming.

(the uneven homogenize of radioactive rays energy)

Below the method that makes the radioactive rays energy that is applied on the molding form the uneven distribution of regulation is described.

For example, as shown in figure 15, when along the thickness direction of molding 1 irradiation radioactive rays, because the arrival amount of radioactive rays energy is according to transmission depth and difference distributes along the inclined foam of thickness direction minimizing thereby can obtain bubble.

In addition, as shown in figure 16, use photomask 2, also can make the part foams only to the prescribed position irradiation radioactive rays of molding 1.When use comprises the photomask 2 that paints, can obtain the part foams that transfer printing has its pattern.The pattern kind has trilateral, stripe-shaped or honeycombed, suitably designs according to purposes to get final product.In addition, the part foams can directly be described to obtain by electron rays or uviolizing.

In addition, as shown in figure 17, use the radioactive rays of energy perviousness, also can be made into inclined foam as 2 pairs of molding irradiations of photomask grayscale mode of grayscale mode.Grayscale mode can be a successive, also can be that (stage) is discontinuous.

In addition, can bubble be distributed changes.For example, as shown in figure 18, in radiation exposure, when the photomask 2 that is provided with triangular shape peristome 3 was slided on molding 1, the direction irradiation time that the summit side 3a of triangular shape slides was short, and base side 3b irradiation time is long.In addition, apparently, make the direction slip of molding 1 that identical effect also be arranged.By irradiation time produce to be distributed, be identically formed the radioactive rays energy distributions in the time of can be with the photomask that uses grayscale mode.And, can obtain various distributions by the shape that changes peristome 3.

As the material of photomask used among Figure 16～Figure 17 2, utilizable have: chrome mask or metal mask, silver chloride glass mask, silver chloride film, half tone mask etc.Utilizable have glass is carried out the mask after the ion etching and the interference fringe of planar lens with light-focusing function is carried out mask etc. after the electron rays scanning.When illumination wavelength was ultraviolet below the 300nm, the base material of photomask preferably used silica glass.The inclined foam or the part foams that utilize the present invention to obtain also can be used as the photomask use.

As the material of photomask used among Figure 18 2, preferably can make acid producing agent produce acid, alkali and produce the material that radioactive rays that agent produces the wavelength of alkali are difficult to transmission, and, preferably can form the material of peristome easily.That for example can enumerate has: cardboard, metal sheet, resin sheet, sheet glass etc.

When using photomask to shine, can adopt modes such as bonding irradiation, projection illumination.For the pattern of transfer printing photomask accurately, irradiates light is preferred directional light uniformly.

As the exposure system that is used to shine directional light, that for example can enumerate has: utilize integrator and put object lens optical system, utilize Fresnel lens optical system, utilize the optical system of perforated plate and scatter plate etc.(with reference to the open homepage of the Network ラ of Co., Ltd. Na ミ: Http:// www.kuranami.co.jp/toku_guide01.htm).

In order to obtain higher homogeneity, preferably utilize integrator and the optical system of putting object lens usually, as the light source that is used in this optical system, preferred short-arc lamp.Short-arc lamp can be enumerated: metal halide lamp, extra-high-pressure mercury vapour lamp, xenon mercuryvapour lamp, sodium vapor lamp, Y line lamp etc.Behind bonding photomask on the molding that the foaminess composition forms, the directional light of irradiation ultraviolet radiation heats makes its foaming, thereby can obtain to have the part foam of the pattern at the wide line/interval of a few μ m.Even also clearly transfer printing of edge this moment.

In addition, also can shine the method for the radioactive rays that produce interference fringe.

(the uneven homogenize of heat energy)

The distribution of heat energy preferably utilizes Heating temperature adjustment.

For example, as shown in figure 19, when the molding 11 after applying the radioactive rays energy is heated,, then can obtain inclined foam if upper surface Heating temperature T1 and lower surface Heating temperature T2 are set at different.Herein, when T1＞T2, the number of bubbles of upper surface side and/or bubble density and lower face side big.

Certainly, when use can change the well heater of Heating temperature on in-plane, can obtain inclined foam along in-plane.

In addition, change the heat energy that is applied on the molding 11 with printer, can make part foams shown in Figure 20 or inclined foam shown in Figure 21 by using the heat record.

Figure 20 utilizes the heat record with printer regional XIIb, XIId, XIIf to be heated and the part foams that obtain.

Figure 21 utilizes the heat record with the printer heating and the right left of heat energy from figure that applies increased and the inclined foam that obtains.

(the uneven homogenize of foaminess composition)

The distribution of the concentration of reducing foaming property functional group concentration in the molding and/or the acid producing agent in the molding (or alkali generation agent) is preferably by using the different multiple foaminess composition of composition to adjust.

Specifically can be listed below.

1) the different flap of blending ratio with decomposability compound and/or acid producing agent (or alkali generation agent) carries out the individual sheets that lamination obtains.

2) be coated on the different coating of blending ratio of decomposability compound and/or acid producing agent (or alkali generation agent) on the support overlappingly and carry out lamination and lamella.

3) the different coating of blending ratio of decomposability compound and/or acid producing agent (or alkali generation agent) is coated on side by side on the support and lamella.

4) flap of foaminess composition and non-foaminess composition is carried out lamination and individual sheets.

5) with the coating of the solution of foaminess composition and non-foaminess composition overlapping be coated on the support and carry out lamination and lamella.

6) coating of the solution of foaminess composition and non-foaminess composition is coated on successively on the support and lamella.

According to 1)～3), as shown in figure 22, can make inclined foam with bubble distribution corresponding with the concentration (concentration of decomposability compound and/or acid producing agent) of foaming composition.In addition, according to 4)～6), as shown in figure 23, can make part foams with bubble distribution corresponding with the concentration (concentration of decomposability compound and/or acid producing agent) of foaming composition.

(three-dimensional bubble distribution)

As the method that the homogenize of bubble skewness is used, the whole bag of tricks of the uneven homogenize of the uneven homogenize of above-mentioned radioactive rays energy, the uneven homogenize of heat energy and foaminess composition can distribute to bubble independently of each other with additive method and exert an influence.Therefore, by with two or more combination the in these methods, can in same foams, carry out three-dimensional control to the direction of its bubble distribution.

(bubble diameter or bubble density)

As mentioned above, number of bubbles and bubble density change easily simultaneously, and bubble density also increases and the number of bubbles trend that bubble density also reduces when reducing when having number of bubbles and increasing.

But,, can either party be changed by adjusting the composition of foaminess composition emphasis.

For example, by improving the glass transition point of foaminess composition, bubble diameter can remained the main bubble density that changes under the smaller state.In addition, by using the foaminess composition of three-dimensional cross-linked property, also bubble diameter can remained the main bubble density that changes under the smaller state.

＜light guide 〉

Light guide of the present invention comprises light guiding section at least, and suitably combined light reflecting part, prism portion, scattering of light portion form as required.

Light guiding section of the present invention has bubble occupied area rate and is predetermined distribution pattern.Preferably have low foamed zones and 1% above high foamed zones below 0.5%.

The bubble occupied area rate of low foamed zones also can be 0%.Because when the bubble occupied area rate of low bubble area is low, can increase the variable quantity of the bubble occupied area rate of light guiding section integral body, so the fully distribution of the light that penetrates from light guiding section of control and make its homogenizing become easy.Like this, can obtain light scattering effect, not need to be provided with in addition scattering of light portion.

The bubble occupied area rate of high foamed zones was preferably more than 15% (being equivalent to about 1.1 times of expansion ratio), more than 30% (being equivalent to about 1.2 times of expansion ratio) more preferably.Because when the bubble occupied area rate of high foamed zones was high, the variable quantity of the bubble occupied area rate of light guiding section integral body can increase, so the fully distribution of the light that penetrates from light guiding section of control and make its homogenizing become easy.But,, also preferably have following bubble occupied area rate of 65% (being equivalent to about 2 times of expansion ratio) even in high foamed zones.Like this, the intensity of light guiding section can become and keep easily.

Preferably have middle foamed zones between low foamed zones and high foamed zones, in middle foamed zones, bubble occupied area rate is from increasing gradually with a side direction of low foamed zones adjacency and a side of high foamed zones adjacency.That is, light guide of the present invention preferably constitutes bubble occupied area rate and increases gradually to high foamed zones from low foamed zones.

Low foamed zones and high foamed zones all can have a plurality of.For example, can constitute:, after bubble occupied area rate increases gradually, reduce gradually again in the low foamed zones of the both sides of high foamed zones configuration.

Bubble in each zone distributes preferably uniform, but also can be the structure that is scattered with the point-like portion that is formed by the micro bubble group.Under the situation that point-like portion is scattered,, become low foamed zones when scattering density hour; When the density of scattering is big, become high foamed zones.In addition, photo-emission part same degree preferred and described later ground has high bubble occupied area rate in each point-like portion.

When using light guide of the present invention, the low foamed zones of light guiding section is configured near the light source position, height is foamed area configurations in the position away from light source.That is, use according to following configuration back: near the locational occupied area rate minimum of light source, and locational bubble occupied area rate farthest be a maximum.

Bubble in the light guiding section preferably is made of the bubble diameter of the scope of 0.1～20 μ m, and more preferably the bubble diameter by the scope of 0.1～10 μ m constitutes.By making bubble diameter is below the wavelength of visible light, thereby is difficult to bubble or point-like portion are observed.Therefore, can omit light diffusion sheet.

Distribute can be by relevant parameters such as setting and light source form and position, light guide areas for concrete bubble in the light guiding section, and uses the optical simulation software of considering Mie scattering and multiple scattering, optical tracking method etc. to carry out optimization.

The bubble occupied area rate of photo-emission part of the present invention is more than 15%, and is preferred more than 30%.When the bubble occupied area rate of photo-emission part is high, can improve reflectivity.But, even photo-emission part also preferably has the bubble occupied area rate below 65%.Like this, the intensity of photo-emission part becomes and keeps easily.

In order to prevent the luminous reflectance spot, the bubble of photo-emission part distributes uniformly preferred.In addition, the bubble in the photo-emission part preferably is made of the bubble diameter of the scope of 0.1～10 μ m, and more preferably the bubble diameter by the scope of 0.2～1 μ m constitutes.

When bubble occupied area rate be 30～65%, when bubble diameter is the scope of 0.2～1 μ m, it is more than 80% that the following thickness of 50 μ m can make full light reflectance.

The bubble occupied area rate of scattering of light of the present invention portion is below 30%, and is preferred below 15%.When the bubble occupied area rate of scattering of light portion is hanged down, can improve full light transmittance, thereby improve the light utilising efficiency.But, even scattering of light portion also preferably has the bubble occupied area rate more than 0.5%.Like this, can bring into play sufficient scattering of light effect.

In order to prevent the luminous reflectance spot, the bubble of scattering of light portion distributes preferably uniform.In addition, the bubble in the photo-emission part preferably is made of the bubble diameter of the scope of 0.1～20 μ m, and more preferably the bubble diameter by the scope of 0.1～10 μ m constitutes.

Particularly, the bubble occupied area rate of scattering of light portion, bubble diameter, thickness setting preferably reach more than 80% for full light reflectance is reached more than 60%.

In order to realize prismatical function, prism of the present invention portion is made of the layer of chiseling V-shaped groove on one surface.Do not need to form bubble in the prism portion, can be by general resin formation.But, also can use the foaminess composition that does not foam.

Below, describe with reference to the embodiment of accompanying drawing light guide of the present invention.But the present invention is not limited to following embodiment.

Figure 30 is the stereographic map of expression first embodiment of the invention (light guide).The light guide of present embodiment only is made of light guiding section 10.Light guiding section 10 is to be made of the foams that form a large amount of bubble B in matrix M, and forms the bubble distribution pattern that the end face 12 of bubble occupied area rate from the end face 11 of incident light light incident side to opposition side increases gradually.That is, near the end face 11 low foamed zones 13, near the end face 12 high foamed zones 14, be middle foamed zones 15 between low foamed zones 13 and the high foamed zones 14.In addition, bubble diameter also can be with 12 increases gradually from end face 11 to end face of bubble occupied area rate.

The light guide of present embodiment is owing to have a this foam distribution pattern, thereby can penetrate roughly light uniformly from whole exit facet 16.

Figure 31 is the example of manufacture method of the light guide of Figure 30.As shown in figure 31, in the molding 1 that is formed with the foaminess composition in advance, use the energy perviousness to be the radioactive rays of the photomask 2 irradiation grayscale mode of grayscale mode, thereby can obtain in matrix M, to have the light guiding section 10 of the bubble B of tilt distribution.

Figure 32 is other examples of manufacture method of the light guide of Fig. 1.Shown in figure 32, in radiation exposure, when the photomask 2 that will be provided with triangle open mouth portion 3 slided (slide) on molding 1, the irradiation time at the position that triangular apex side 3a slides shortened, and the irradiation time of base side 3b increases.

In addition, molding 1 is slided and also can obtain same effect certainly.By irradiation time produce to be distributed, be identically formed the radioactive rays energy distributions in the time of can be with the photomask that uses grayscale mode, obtain to have the light guiding section 10 of the bubble of tilt distribution.

Figure 33 is the stereographic map of expression second embodiment of the present invention (light guide).The light guide of present embodiment also is only to be made of light guiding section 10.Light guiding section 10 is made of the foams that are formed with a large amount of point-like D of portion in matrix M, and the distribution of the D of point-like portion increases to the end face 12 of opposition side gradually from the end face 11 of incident light light incident side.Because each D of point-like portion is the aggregate of a large amount of bubble B,, form the bubble distribution pattern that the end face 12 of bubble occupied area rate from the end face 11 of incident light incident one side to opposition side increases gradually so the angle that distributes from bubble is observed light guiding section 10 integral body.That is, near the of end face 11 is high foamed zones 14 near the end face 12 for low foamed zones 13, is middle foamed zones 15 between low foamed zones 13 and the high foamed zones 14.

The light guide of present embodiment is owing to have a this bubble distribution pattern, thereby penetrates roughly light uniformly from whole exit facet 16.In addition, in order to control the visibility of each D of point-like portion, also lamination scattering of light portion as required.

Figure 34 is the stereographic map of expression the 3rd embodiment of the present invention (light guide).The light guide of present embodiment only is made of light guiding section 10, but light guiding section 10 is the layered product of foams 10a and transparent resin 10b.

The light guiding section 10 of the foam 10a and first embodiment is roughly the same.That is, form, form the bubble distribution pattern that the end face 12a of bubble occupied area rate from the end face 11a of incident light incident one side to opposition side increases gradually by the foams that in matrix M, are formed with a large amount of bubble B.

A kind of transparent resin 10b does not have bubble.Material as transparent resin 10b, for example preferred: acrylic resin or methacrylic resins such as methyl methacrylate, annular olefin resin such as norbornylene, polycarbonate resin, cellulose families such as cellulosetri-acetate, phenylethylene resin series, and the hybrid resin that is mixed with two or more these materials.

In the present embodiment, near the of end face 11a, 11b is low foamed zones 13, and near the of end face 12a, 12b is high foamed zones 14, is middle foamed zones 15 between low foamed zones 13 and the high foamed zones 14.In addition, identical with the light guiding section 10 of first embodiment, to end face 12a, bubble occupied area rate and bubble diameter also can increase simultaneously gradually from end face 11a.

The light guide of present embodiment is owing to have a this bubble distribution pattern, thereby can penetrate roughly light uniformly from whole exit facet 16 (upper surface of transparent resin 10b).

The foams 10a that the light guide of Figure 34 can obtain in the same manner by the light guide with first embodiment, transparent resin 10b is bonding makes.In addition, as shown in figure 35, can adopt the mold-in injection manufacturing process to make.

As shown in figure 35, in the mold-in injection manufacturing process, at first, the sheet 4 of the transparent resin system of rolling is passed (operation (1)) between mould 5a, the 5b that injection molding is used.Then, clamp the sheet 4 of transparent resin system, in mould 5a, 5b, inject filling-foam composition 6, make the sheet 4 and foamable resin composition integrated (operation (2)) of transparent resin system with mould 5a, 5b.And, the foaminess composition 6 of filling is solidified, then mold removal 5a, 5b (operation (3)).Then, carry the sheet 4 (operation (4)) of transparent resin system.Below, by repeating operation (1)～(4), can obtain the sheet 4 and the incorporate layered product of foaminess composition of transparent resin system in a large number.To this layered product, by applying radioactive rays energy and heat energy, make it, thereby can obtain the light guide of Figure 34 with predetermined pattern foaming.In addition, before or after foamed process, need to shear respectively the layered product that connects into drum.

Figure 36 is the stereographic map of expression the 4th embodiment of the present invention (light guide).Though the light guide of present embodiment also is only to be made of light guiding section 10, light guiding section 10 is the layered product of foams 10a and transparent resin 10b.

The light guiding section 10 of the foams 10a and second embodiment is roughly the same.That is, foams 10a is formed by the foams that form a large amount of point-like D of portion in matrix M, and the end face 12a of the distribution of the D of point-like portion from the end face 11a of incident light incident one side to opposition side increases gradually.Each D of point-like portion is the aggregate of a large amount of bubble B.

A kind of transparent resin 10b does not have bubble.As the material of transparent resin 10b, can use the material identical with the transparent resin 10b of the 3rd embodiment.

It seems from bubble distribution aspect, whole light guiding section 10 form bubble occupied area rate from end face 11a, the 11b of incident light incident one side to the end face 12a of opposition side, the bubble distribution pattern that 12b increases gradually.

In the present embodiment, near the of end face 11a, 11b is low foamed zones 13, and near the of end face 12a, 12b is high foamed zones 14, is middle foamed zones 15 between low foamed zones 13 and the high foamed zones 14.In addition, identical with the light guiding section 10 of first embodiment, to end face 12a, bubble occupied area rate and bubble diameter also can increase simultaneously gradually from end face 11a.

The light guide of present embodiment is owing to have a this bubble distribution pattern, thereby can penetrate roughly light uniformly from whole exit facet 16 (upper surface of transparent resin 10b).

The light guide of Figure 36 can by will be with the same foams 10a that obtains of the light guide of second embodiment, transparent resin 10b is bonding makes.In addition, identical with the 3rd embodiment, can adopt the mold-in injection manufacturing process to make.

Figure 37 is the stereographic map of expression the 5th embodiment of the present invention (light guide).The light guide of present embodiment is connected the photo-emission part 20 that is provided with by light guiding section 10 and with its three end faces and constitutes.As light guiding section 10, can suitably adopt the light guiding section 10 in first～the 4th embodiment.By around the end face of light guiding section 10, photo-emission part 20 being set, can improve the light utilising efficiency.

Manufacture method as the light guide of present embodiment can be listed below method: on the tabular shaping thing of foaminess composition, photomask is covered want to form the zone of light guiding section 10, and the irradiation radioactive rays, heating makes its foaming then.Promptly, quantity of radiation across the part of photomask is controlled, become light guiding section 10, and evenly and fully shine, thereby form the photo-emission part 20 that makes a large amount of micro bubble groups evenly be present in inside to high-density from the quantity of radiation on every side that photomask exposes with bubble distribution pattern.

Figure 38 is the stereographic map of expression the 6th embodiment of the present invention (light guide).The light guide of present embodiment is connected the photo-emission part 20 that is provided with and constitutes by light guiding section 10, with the opposite face of its exit facet 16.Light guiding section 10 can suitably adopt the light guiding section 10 in first～the 4th embodiment.By photo-emission part 20 is set, can improve the light utilising efficiency.

Manufacture method as the light guide of present embodiment, can be listed below manufacture method: the tabular shaping thing of preparing two foaminess compositions, shine radioactive rays across photomask (slant pattern etc.) to one of them, radioactive rays are shone on whole surface to another equably, then lamination both make it integrated, and the heating make its foaming, thereby make light guide.Promptly, control is across the quantity of radiation of the part of photomask, formation has the light guiding section 10 of bubble distribution pattern, and evenly and fully shine quantity of radiation to the part of not using the photomask uniform irradiation, evenly be present in inner photo-emission part 20 to high-density thereby form a large amount of micro-bubble groups.

Perhaps, as additive method, can pass through across the tabular shaping thing irradiation radioactive rays of photomask (slant pattern) to the foaminess composition, and shine radioactive rays with the more shallow irradiation degree of depth to its back surface layer, heating makes its foaming, thereby makes light guide.That is, become the light guiding section 10 with bubble distribution pattern across the part of photomask, its rear side is owing to be subjected to the partial irradiation of irradiation energy, thereby forms the photo-emission part 20 that evenly has the micro bubble group in the top layer to high-density.

Figure 39 is the stereographic map of expression the 7th embodiment of the present invention (light guide).The light guide of present embodiment is made of with the prism portion 30 that is connected its exit facet 16 settings light guiding section 10.As light guiding section 10, can suitably adopt the light guiding section 10 of first～the 4th embodiment.

Manufacture method as the light guide of present embodiment, can be listed below manufacture method: translucent resin is shaped, then, from mould, do not taking out under the situation of translucent resin, put into the tabular shaping thing that carries out light-struck foaminess composition across photomask (tilt mode) again, and heating and pressurizing, make its foaming simultaneously laminated, thereby make light guide.After foaming, take out, can obtain to have the light guiding section of bubble distribution pattern and the incorporate light guide of layers of prisms that forms V-shaped groove on its surface from mould.

In addition, can adopt the mold-in injection manufacturing process that in the 3rd embodiment, illustrates.At this moment, can use prismatic lens to replace the sheet 4 of the transparent resin system among Figure 35.

Light guide of the present invention can form above-mentioned the 5th～the 7th embodiment appropriate combination.For example also can have and three end faces of light guiding section 10 and the photo-emission part 20 that joins with the opposite face of its exit facet 16.In addition, also can be the structure that on this structure, further increases prism portion 30.

＜surface illuminating device 〉

Surface illuminating device of the present invention comprise the invention described above light guide and with the plane of incidence side joint of this light guide light source of configuration closely even contiguously.As light source, can suitably adopt line source or photodiode electric light sources such as (LED) such as cold-cathode tube.

Surface illuminating device of the present invention can be used in the various display unit identical with existing surface illuminating device.For example, can be used as the back light of the employed liquid crystal indicator of indicating meter of televisor or portable phone, Personal Computer, automobile etc. or headlight and use.In addition, can be used as the internal irradiation illumination of the display unit of using in the way-finding sign board of station or communal facility etc. or billboard, the traffic mark etc. and using.And, also can be used as the general lighting that uses in office or the family and use.

Below, describe with reference to the embodiment of accompanying drawing surface illuminating device of the present invention.But the present invention is not limited to following embodiment.

Figure 40 is the stereographic map of expression the 8th embodiment of the present invention (surface illuminating device).The surface illuminating device of present embodiment by light guide 100, with the plane of incidence of light guide 100 near in addition the light source 200,200 that is provided with contiguously constitute.In the present embodiment,, used a plurality of (preferred 3～4 lamps) white chip LED as light source 200.

Light guide 100 is made of light guiding section 10 and reflecting part 20.Because light guiding section 10 is identical with the light guiding section 10 of first embodiment, so the symbol identical to identical integrant mark, omission specifies.Reflecting part 20 is made of the end face photo-emission part 20a of three end faces that are connected in light guiding section 10 and the 20b of dorsal light reflex portion that is connected in the opposite face of exit facet 16.

Surface illuminating device in the present embodiment can be made with for example following step.At first, as shown in figure 41, prepare plate 50, this plate 50 is the foaminess composition to be configured as tabular, suitably shines radioactive rays again, makes inner 51 to become light guiding section 10, and makes three sides 52 become end face photo-emission part 20a.On the other hand, as shown in figure 42, be ready to shine the plate 53 that forms the dorsal light reflex 20b of portion behind the radioactive rays.

Then, by with the plate 50 of Figure 41 with heat simultaneously after the plate 53 of Figure 42 overlaps and squeeze, form two plates integrated and foam, make light guide 100.

Then, with the plane of incidence 11 of light guiding section 10 fixed light source 200,200 at certain intervals relatively, thereby obtain the surface illuminating device of present embodiment.

In addition, fixed light source 200,200 o'clock, with the slit of light leak with coverings such as white seal gums.In addition,, also can use cold-cathode tube to replace white chip LED side by side, but white chip LED is easy to miniaturization as light source 200,200.

Figure 43 is the stereographic map of expression ninth embodiment of the invention (surface illuminating device).The surface illuminating device of present embodiment be by light guide 100 with the plane of incidence 11 of light guide 100 near in addition contact and the light source 200 that is provided with constitutes.In the present embodiment, light source 200 uses cold-cathode tube.

Light guide 100 is made of light guiding section 10 and reflecting part 20.Because light guiding section 10 is identical with the light guiding section 10 of first embodiment, so, omit its detailed description to the identical identical symbol of composed component mark.Reflecting part 20 comprises: the end face photo-emission part 20a that is connected with three end faces of light guiding section 10, the 20b of dorsal light reflex portion that is connected with the opposite face of exit facet 16 and the light source reflecting part 20c that covers light source 200 settings in the plane of incidence 11 sides of light guiding section 10.On this light source reflecting part 20c, be provided with the plane of incidence 11 side openings U word groove shape run through groove 20d, portion inserts light source 200 within it.

Surface illuminating device in the present embodiment can be made by for example following step.At first, as shown in figure 44, prepare plate 50, this plate 50 is the foaminess composition to be configured as tabular, suitably shines radioactive rays again, makes inner 51 to become light guiding section 10, and makes three sides 52 become end face photo-emission part 20a and end face photo-emission part 20c.On the other hand, as shown in figure 45, be ready to shine the plate 53 that forms the dorsal light reflex 20b of portion behind the radioactive rays.

Then, the plate 50 of Figure 44 is overlapped with the plate 53 of Figure 45, heat and squeeze, two plates are formed one and make its foaming, then wear and run through groove 20d, thereby make light guide 100.

Then, by insertion light source 200 in through slot 20d, thus the surface illuminating device of acquisition present embodiment.

In the present embodiment, because light source 200 is built among the interior through slot 20d of light source reflecting part 20c, so almost can prevent fully from the cold-cathode tube light leak.In addition, as light source 200, can replace cold-cathode tube with white chip LED.

Figure 46 is the stereographic map of expression the tenth embodiment of the present invention (surface illuminating device).The surface illuminating device of present embodiment by light guide 100, with the plane of incidence of light guide 100 near in addition the light source 200,200 that is provided with contiguously constitute.In the present embodiment,, used a pair of white chip LED as light source 200.Light guide 100 is made of light guiding section 10 and reflecting part 20.

Light guiding section 10 is connected the introduction part 10d that is provided with and constitutes by the 10c of outgoing portion and with the plane of incidence 11b of the 10c of outgoing portion.The structure of the 10c of outgoing portion is identical with the light guiding section 10 of first embodiment, so the symbol identical to identical component parts mark, omission specifies.

Introduction part 10d forms bubble occupied area rate and increases the bubble distribution pattern that reduces gradually then gradually along the plane of incidence 11a (not shown) of plane of incidence 11b from plane of incidence 11a to opposition side.That is, near the of two plane of incidence 11a is low foamed zones 13, and central part is high foamed zones 14, and (both sides of high foamed zones 14) are middle foamed zones 15 between low foamed zones 13 and the high foamed zones 14.In addition, bubble diameter also can increase and decrease synchronously with the increase and decrease of bubble occupied area rate.Introduction part 10d can penetrate roughly the state of light uniformly owing to have this bubble distribution pattern to plane of incidence 11b thereby form.Consequently the whole exit facet 16 from the 10c of outgoing portion penetrates roughly light uniformly.

Reflecting part 20 comprises: the end face photo-emission part 20a that is connected with three end faces of the 10c of outgoing portion, the importing reflecting part 20d, the 20b of dorsal light reflex portion that is connected with the opposite face of exit facet 16 that are connected with the opposition side end face of the plane of incidence 11b of introduction part 10d.

Surface illuminating device in the present embodiment can be made by for example following step.At first, as shown in figure 47, prepare plate 50, this plate 50 is the foaminess composition to be configured as tabular, suitably shines radioactive rays again, makes inner 51 to become light guiding section 10, and makes four sides 52 become end face photo-emission part 20a and end face photo-emission part 20c.On the other hand, as shown in figure 48, be ready to shine the plate 53 that forms the dorsal light reflex 20b of portion behind the radioactive rays.

Then, the plate 50 of Figure 47 is overlapped with the plate 53 of Figure 48, heat and squeeze, two plates are formed one and make its foaming, then remove the part 52a that is connected with a pair of plane of incidence 11a of side 52, thereby make light guide 100.

Then, with each plane of incidence 11a over against ground fixed light source 200,200, thereby obtain the surface illuminating device of present embodiment.

In addition, fixed light source 200,200 o'clock, the slit that also can block light leak with white strip of paper used for sealing etc.In addition, (can be the photo-emission part that is made of foam, also can be existing known reflector plate photo-emission part also can be set on introduction part 10d.)。

Embodiment

The present invention is described in detail by following embodiment, but the present invention is not limited to these embodiment.In addition, short of specified otherwise, " part " in the example reaches " % " and represents that respectively " mass parts " reaches " quality % ".

＜embodiment 1 〉

(1) foaminess composition

Use following foaminess composition A: relatively as 00 part of the copolymer 1 of tert-butyl acrylate (20%), methacrylic tert-butyl acrylate (40%) and the methyl methacrylate (40%) of decomposability compound, mixing is as 3 parts of two (4-tert-butyl-phenyl) salt compounded of iodine of the perfluorinated butane sulfonic acid of the serial acid producing agent of salt compounded of iodine (trade mark: BBI-109, ミ De リ chemistry system).

(2) preliminary forming operation

With the diluent of MEK/ ethyl acetate=65/35 (mass ratio) the foaminess composition of above-mentioned ratio of mixture is modulated into 25% solution, this solution is used as coating fluid.Use opening (clearance) be 300 μ m applicator with this coating fluid be coated on thickness be 75 μ m by silicon PET (trade mark: MR-75, the Port リ エ ス テ of Mitsubishi Le system) on the silicon treated side of the support of Gou Chenging, and in 110 ℃ freeze-day with constant temperature machine, placed 10 minutes, evaporation removes and desolvates.After sample taken out, go up the release-coated layer from the freeze-day with constant temperature machine, obtain the film that thickness is 45 μ m from silicon PET.Cut 10 and make it stacked with 5cm * 6cm from this film, with 10cm * 10cm and thickness is that the SUS plate holder of 1mm is held this duplexer, use manual squeezing machine (the Mini TEST PRESS-10 that trade mark: TOYOSEIKI makes), this laminated samples is being applied under the 6MPa pressure status with 150 ℃ of squeezing shapings 3 minutes.After pressure relief, under the state of holding with the SUS plate holder, from squeezing machine, take out sample, use the air naturally cooling, from the SUS plate, take off tabular foaminess formed product composition.

(3) uviolizing

To the tabular foaming composition molding of described operation (2), with metal halide lamp (trade mark: ア イ グ ラ Off イ Star Network (strain) system, ultraviolet curing is with many metalized lamps M03-L31) as light source, with 2000mJ/cm ²The irradiation light amount is respectively from upper and lower surface irradiation ultraviolet ray.

(4) foamed process

With 10cm * 10cm and thickness is tabular foaming composition molding after the SUS plate holder of 1mm is held the irradiation ultraviolet radiation that obtains by described operation (3), made its foaming in 2 minutes simultaneously using manual squeezing machine (trade mark: TOYOSEIKI makes, Mini TEST PRESS-10) that this laminated samples is applied under the 4MPa pressure status to squeeze with 130 ℃.After pressure relief, remain on and from squeezing machine, take out sample under the state of holding with the SUS plate holder, use the air naturally cooling, from the SUS plate, take off the slab foam body.

(5) foam structure evaluation

The foamy structure of the foams that obtain in order to confirm is observed its section.Sample is freezing and cut off in liquid nitrogen, on the foams section, carry out golden vapor deposition treatment, utilize scanning electron microscope (trade mark: S-510, the Hitachi makes) to observe the cross-section structure of this gold evaporation face.Cross sectional photograph as shown in Figure 5.Select 100 bubbles at random from the observation image (enlargement ratio: 3000 times) of foamed resin layer section, try to achieve the mean value of its diameter, thereby obtain mean air bubble diameter.Expansion ratio so obtains: at room temperature utilize Archimedes's method to measure the density (A) of foams and the density (B) when foams being dissolved in the solvent once more film forming and being in foamed state not, try to achieve expansion ratio by B/A.The thickness of foams can be used milscale, and (trade mark: Mitutoyo makes, and MCD-25M) measures.The foams that obtained are that mean air bubble diameter is that 0.3 μ m, expansion ratio are that 1.3 times, thickness are the slab foam body of 500 μ m.

＜embodiment 2 〉

Except in foamed process, laminated samples being applied the pressure of 2MPa, use the method identical to make foams with embodiment 1.Cross sectional photograph as shown in Figure 6.

In the same manner foam structure is estimated with embodiment 1, the result is, the foams that obtained are that mean air bubble diameter is that 0.1 μ m, expansion ratio are that 1.8 times, thickness are the slab foam body of 700 μ m.

＜embodiment 3 〉

(1) foaminess composition

Use the material identical with embodiment 1.

(2) preliminary forming operation

Make the coating layer that has support in the same manner with embodiment 1, it is to be provided with the coating layer that thickness is the foaminess composition of 45 μ m on silicon PET.

(3) uviolizing

With metal halide lamp (trade mark: ア イ グ ラ Off イ Star Network (strain) is made, ultraviolet curing with many metalized lamps M03-L31) as light source, with 2000mJ/cm ²The irradiation light amount from the coating layer irradiation ultraviolet radiation of the band support of painting layer surface side direction (2).Irradiation ultraviolet radiation is afterwards from silicon PET release-coated layer, thereby the foaming composition film of uviolizing is finished in acquisition.

(4) foaming and molding operation

Cut the film of 10 5cm * 6cm and make it stacked from the film that obtains by (3), use and be provided with bottom surface shown in Figure 2 manual squeezing machine (trade mark: TOYOSEIKI manufacturing as the rectangular parallelepiped molding die of 5cm * 6cm, Mini TEST PRESS-10), this laminated samples is being applied under the 4MPa pressure status, this layered product squeezing shaping was being made its foaming in 2 minutes with 130 ℃.After pressure relief, mould is taken out and uses the air naturally cooling from squeezing machine, when die temperature reaches 40 ℃ of left and right sides, the foams molding is taken out from the rectangular parallelepiped molding die.

(5) foam structure evaluation

In the same manner the structure of foam is estimated with embodiment 1, the result is, the foams that obtained are that mean air bubble diameter is that 0.2 μ m, expansion ratio are that 1.2 times, thickness are the slab foam body of 450 μ m.

＜embodiment 4 〉

(1) foaminess composition

Use following foaminess composition B: relatively as 00 part of the copolymer 1 of tert-butyl acrylate (60%), methyl methacrylate (30%) and the methacrylic acid (10%) of decomposability compound, mixing forms for 3 parts as two (4-tert-butyl-phenyl) salt compounded of iodine of perfluorinated butane sulfonic acid (trade mark: BBI-109, ミ De リ chemistry is made) of salt compounded of iodine series acid producing agent.

(2) preliminary forming operation

The foaminess composition of above-mentioned ratio of mixture is modulated into 25% solution with ethyl acetate, this solution is used as coating fluid.Use opening (clearance) be 300 μ m applicator with this coating fluid be coated on thickness be 75 μ m by silicon PET (trade mark: MR-75, the manufacturing of the Port リ エ ス テ of Mitsubishi Le) on the silicon treated side of the support that constitutes, and in 110 ℃ freeze-day with constant temperature machine, placed 10 minutes, evaporation removes and desolvates, make the coating layer of band support, it is to be provided with the coating layer that thickness is the foaminess composition of 45 μ m on silicon PET.

(3) uviolizing

With metal halide lamp (trade mark: ア イ グ ラ Off イ Star Network (strain) is made, ultraviolet curing with many metalized lamps M03-L31) as light source, with 1000mJ/cm ²The irradiation light amount from the coating layer irradiation ultraviolet radiation of painting layer surface side to the band support of (2).Go up the release-coated layer from silicon PET after the uviolizing, thereby obtain to finish the foaming composition film of uviolizing.

(4) foaming and molding operation

Cut the film of 10 5cm * 6cm and make it stacked from the film that obtains by (3), use and be provided with bottom surface shown in Figure 7 manual squeezing machine (trade mark: TOYOSEIKI manufacturing as the rectangular parallelepiped molding die of 5cm * 6cm, Mini TEST PRESS-10), this laminated samples is being applied under the 4MPa pressure status, this layered product squeezing shaping was being made its foaming in 2 minutes with 130 ℃.Keeping under the 4MPa pressure status then, from the water coolant introduction part importing water coolant of rectangular parallelepiped molding die.When die temperature reaches 50 ℃ of left and right sides, mould is taken out from manual squeezing machine, make under the state of flow of cooling water, when reaching 40 ℃ of left and right sides, from the rectangular parallelepiped molding die, take out the foams molding.

(5) foam structure evaluation

In the same manner the foam structure is estimated with embodiment 1, the result is, the foams of acquisition are that mean air bubble diameter is that 0.1 μ m, expansion ratio are that 1.1 times, thickness are the slab foam body of 450 μ m.

＜embodiment 5 〉

(1) foaminess composition

Use following foaminess composition C: relative 20 parts of tert-butyl acrylate monomers, 40 parts of methacrylic tert-butyl acrylate monomers, 40 parts of methyl methacrylates as the decomposability compound, mixing is as 3 parts of two (4-tert-butyl-phenyl) salt compounded of iodine of the perfluorinated butane sulfonic acid of the serial acid producing agent of salt compounded of iodine (trade mark: BBI-109, ミ De リ chemistry is made).

(2) preliminary forming operation (uviolizing operation)

The monomer of (1) and acid producing agent mixture are injected the counterdie of rectangular parallelepiped molding die shown in Figure 2, face from it, with metal halide lamp (trade mark: ア イ グ ラ Off イ Star Network (strain) is made, ultraviolet curing with many metalized lamps M03-L31) as light source, with 3000mJ/cm ²The irradiation light amount respectively from upper and lower surface irradiation ultraviolet ray.

(3) foaming and molding operation

As shown in Figure 2, on the injection mold that adds the cured resin that obtains by (2), patrix is installed, and is arranged on the manual squeezing machine (trade mark: TOYOSEIKI makes Mini TESTPRESS-10).Made its foaming in 2 minutes this laminated samples being applied under the 4MPa pressure status this layered product is shaped with 130 ℃ of squeezings.Then under the pressure status that keeps 4MPa, from the water coolant introduction part importing water coolant of mould.When die temperature reaches 40 ℃ of left and right sides, mould is taken out from manual squeezing machine, the foams molding is taken out from the rectangular parallelepiped molding die.

(4) foam structure evaluation

In the same manner the foam structure is estimated with embodiment 1, the result is, the foams that obtained are that mean air bubble diameter is that 0.3 μ m, expansion ratio are that 1.3 times, thickness are the slab foam body of 500 μ m.

＜embodiment 6 〉

(1) foaminess composition

Use the material identical with embodiment 1.

(2) preliminary forming operation and uviolizing operation

Obtain to finish the foaming composition film of uviolizing in the same manner with embodiment 3.

(3) foaming and molding operation

To be cut into 5cm * 6cm by the foaming composition film of finishing uviolizing that (2) obtain, the thickness that will be cut into 5cm * 6cm is that (Supreme Being people makes the POLYCARBONATE SHEET of 1mm, パ Application ラ イ ト シ one ト PC-1151) stacked, squeeze in the same manner with embodiment 1 and to make its foaming.

(4) foam structure evaluation

In the same manner the foam structure is estimated with embodiment 1, the result is, the foams that obtained are that to be formed with mean air bubble diameter on POLYCARBONATE SHEET be that 0.3 μ m, expansion ratio are that 1.3 times, thickness are the foams of the foam layer of 45 μ m.

＜comparative example 1 〉

In foamed process, not distinguishingly to tabular foaminess composition pressurization, but under atmospheric pressure state, be suspended in the constent temperature heater (freeze-day with constant temperature machine), under 130 ℃, make its foaming 2 minutes, except that above-mentioned, identical with embodiment 1.The foam cross sectional photograph that is obtained as shown in Figure 8.This foam is to have the foams that a large amount of bubble diameters surpasses the large bubble of 100 μ m.And owing to can not obtain the good tabular plane foams of outward appearance, but crooked atypic foam also is rough cacoplastic foams so become the surface.

＜comparative example 2 〉

(1) foaminess composition

Use the material identical with embodiment.

(2) preliminary forming operation

With embodiment 1 in the same manner, peel off foaminess composition coating layer from silicon PET, obtaining thickness is the film of 45 μ m.Cut from this film and to be 5cm * 6cm, and it is identical with embodiment 6, POLYCARBONATE SHEET is stacked, use the thickness of 10cm * 10cm to hold this duplexer then as the SUS plate holder of 1mm, use manual squeezing machine (trade mark: TOYOSEIKI makes Mini TEST PRESS-10), this laminated samples is being applied under the 4MPa pressure status, this layered product squeezing had been shaped 3 minutes with 150 ℃.After pressure relief, under the state of holding sample with the SUS plate holder, from squeezing machine, take out, use the air naturally cooling, be that the foaminess composition layer of 45 μ m is laminated to the molding that forms on the POLYCARBONATE SHEET and takes off from the SUS plate with thickness.

(3) uviolizing

From being formed on a side of the foaminess composition layer on the POLYCARBONATE SHEET, with metal halide lamp (trade mark: ア イ グ ラ Off イ Star Network (strain) is made, ultraviolet curing with many metalized lamps M03-L31) as light source, with 2000mJ/cm ²Irradiation light amount irradiation ultraviolet radiation.

(4) foaming and molding operation

The molding of above-mentioned uviolizing is suspended in the constent temperature heater (freeze-day with constant temperature machine) under the atmospheric pressure state that does not have pressurization, foamed 2 minutes down, take out, use the air naturally cooling from constent temperature heater (freeze-day with constant temperature machine) at 130 ℃.

(5) outward appearance of foams

The foams that obtained have the part that a plurality of foaming layers strip down from the support of POLYCARBONATE SHEET, promptly occurring diameter on support is the concavo-convex body of semisphere of several mm, film can not be formed well the shape of support, can not make laminated even fine foams, thereby form cacoplastic foams.

＜reference example 〉

Use the foaminess composition identical, pass through preliminary forming operation and the uviolizing operation identical, use the foamed process identical to make its foaming with embodiment 3 with embodiment 4 with embodiment 4.Promptly in the refrigerating work procedure of embodiment 4, cool off again after the pressure relief in advance.This foam contain in a large number by visual be the large bubble of observable several millimeters bubble diameter, can not obtain the good tabular plane foams of outward appearance, but the unsetting foams of distorting, and be to occur concavo-convex cacoplastic foams from the teeth outwards.

The above results is summarized in table 1 and table 2.

Table 1

	Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4	Embodiment 5	Embodiment 6
							The foaminess composition	A	A	A	B	C	A
The preliminary forming condition	Coating method+plate squeezing	Coating method+plate squeezing	Coating method	Coating method	Injection moulding	Coating method
							The UV illuminate condition	2000mJ/cm 2Shadow surface: upper and lower surface	2000mJ/cm 2Shadow surface: upper and lower surface	2000mJ/cm 2Shadow surface: coating aspect	1000mJ/cm 2Shadow surface: coating aspect	3000mJ/cm 2Shadow surface: injection mold upper surface	2000mJ/cm 2Shadow surface: coating aspect
Foaming condition	130 ℃ of plate squeezing 4Mpa 2 minutes	130 ℃ of plate squeezing 2MPa 2 minutes	130 ℃ of mould 4MPa 2 minutes	130 ℃ of mould 4MPa 2 minutes	130 ℃ of mould 4MPa 2 minutes	130 ℃ of plate squeezing 4MPa 2 minutes
							Cooling conditions	Pressure relief	Pressure relief	Pressure relief	The pressurized water cooling	Pressure relief	Pressure relief
The foams outward appearance	Well	Well	Well	Well	Well	Well (PC lamination)
							Bubble diameter (μ m)	0.3	1.0	0.2	0.1	0.3	0.3
Expansion ratio	1.3	1.8	1.2	1.1	1.3	1.3
							Thickness (μ m)	500	800	450	450	500	45

Table 2

	Comparative example 1	Comparative example 2	Reference example
				The foaminess composition	A	A	B
The preliminary forming condition	Coating method+plate squeezing	Coating method+plate squeezing	Coating method
				The UV illuminate condition	2000mJ/cm 2Shadow surface: upper and lower surface	2000mJ/cm 2Shadow surface: foaminess composition aspect	2000mJ/cm 2Shadow surface: coating aspect
Foaming condition	130 ℃ of normal pressures 2 minutes	130 ℃ of normal pressures 2 minutes	Mould 4MPa, 130 ℃ 2 minutes
				Cooling conditions	Normal pressure (pressure is open)	Normal pressure (pressure is open)	Pressure is open
The foams outward appearance	It is bad to be shaped	Bad (PC lamination) is shaped	It is bad to be shaped
				Bubble diameter (μ m)	The inner existence more than the 100 μ m	There are several mm in inside	There are several mm in inside

＜embodiment 7-1 〉

The making of＜foams sheet 〉

(1) formation of coating layer

Relatively as 00 part of the copolymer 1 of tert-butyl acrylate (60 weight %), methacrylic tert-butyl acrylate (30 weight %) and the methacrylic acid (10 weight %) of decomposability compound, mixing is as two (4-tert-butyl-phenyl) salt compounded of iodine (trade marks: BBI-109 of perfluorinated butane sulfonic acid of salt compounded of iodine series acid producing agent, the manufacturing of ミ De リ chemistry) 3 part, this mixture is dissolved in the ethyl acetate, be adjusted to the solids component amount and be 25% solution, this solution is used as coating fluid.

Opening (gap) width that uses coating usefulness is that the paint daubs of 300 μ m is applied to this coating fluid on the single face of the support that the transparent polyethylene terephthalate that thickness is 75 μ m (trade mark: Le ミ ラ-75-T60, パ Na Star Network is made) constitutes.Then, in being 110 ℃ freeze-day with constant temperature machine, temperature placed 5 minutes the evaporative removal solvent immediately.On the support of polyethylene terephthalate, form the water white transparency coating layer of film like.The thickness of coating layer is adjusted in the scope of 40～50 μ m.

(2) uviolizing

On the coating layer that forms by described operation (1), fitting has the chrome mask (silica glass system) of line and space (line and space) pattern, carries out uviolizing from the photomask side.Line and space pattern use is the line (width is 100 μ m) of ultraviolet transmissive and the ultraviolet ray line of transmissive (gap: the pattern that forms of arrangement alternately mutually width 100 μ m) not fully.As light source, make 2000mJ/cm with metal halide lamp ²Irradiation light amount irradiation ultraviolet radiation.After irradiation, take off chrome mask, the coating layer of acquisition and operation (1) coating layer afterwards is as broad as long, still is water white.

(3) utilize thermal treatment to foam

To peel off from support by the coating layer that described operation (2) obtains, this single film will be handled 5 minutes at the thermostatted internal heating that remains 110 ℃ of temperature.When using microscope (trade mark: KH-2700, HiRox makes) when the film after the heating is observed, can confirm, as shown in figure 24, uviolizing portion 10 is that live width is the white foaming portion of the wire of 100 μ m, and irradiation portion 20 still is not a water white not foaming portion.

(4) evaluation of foamy structure

Utilize scanning electron microscope (trade mark: S-510, the Hitachi makes) to observe affirmation by the foamy structure in the uviolizing portion 10 of the film of described operation (3) acquisition.To described film is dipped in the liquid nitrogen and freeze cracking after section carry out metal evaporation and handle, use scanning electron microscope (trade mark: S-510, the Hitachi makes) to observe section then.This section as shown in figure 25.

By the bubble diameter and the bubble density that go out from the observation image calculation foamy structure is estimated.Particularly, from observe image (enlarging multiplying power is 5000 times), select the inner zone that has the bubble population that amounts to 150 left and right sides bubbles at random, these bubble populations and matrix are in addition carried out binary conversion treatment, use image analysis apparatus (trade mark: image analyzer V10, TOYOBO manufacturing) that bubble diameter and bubble density are estimated then.At this moment, the mean value of asking for bubble diameter is as bubble diameter, and tries to achieve bubble occupied area rate (%) as bubble density.

Consequently, the bubble diameter of the R1 of uviolizing portion of the wire of live width 100 μ m white foaming portion is 0.25 μ m, and bubble occupied area rate is 28%.On the other hand, do not observe bubble among the water white not irradiation R0 of portion.Like this, can obtain to have the partial foaming body that bubble diameter is the following foamed zones of 1 μ m.

＜embodiment 7-2 〉

Similarly make foams with embodiment 7-1 with bubble distribution.But in the operation (2) of embodiment 7-1, using diameter is the chrome mask replacement line and the space pattern of the dot pattern of 3 μ m, and what ultraviolet ray was used is the uniform directional light that penetrates from Y line lamp (peak wavelength is 214nm), with 1J/cm ²The irradiation light amount shine.

As shown in figure 26, the diameter of the foams that obtained is that the R1 of uviolizing portion of 3 μ m is the point-like white foam.In addition, its foamy structure is identical with embodiment 7-1.On the other hand, the R0 of irradiation portion is not water white, and does not observe bubble.Like this, by using directional light, can obtain to make the part foam of the partial foaming of a few μ m levels.

＜embodiment 7-3 〉

Similarly make foams with embodiment 7-1 with bubble distribution.But, in the operation (2) of embodiment 7-1, use the photomask of successive greyscale pattern to replace line and space pattern.As shown in figure 27, the foams that obtained along foaming gradually to a low side from the high side of the transmissivity of mask with bleaching.As shown in figure 28, in the process that foaming structure bleaches, (a～e) estimate can confirm in the same film that bubble diameter and bubble occupation density increase gradually to representational 5 points.Particularly, each foamy structure that a～e is ordered is respectively: (a) bubble diameter is 0.17 μ m, and bubble occupied area rate is 4%; (b) bubble diameter is 0.22 μ m, and bubble occupied area rate is 9%; (c) bubble diameter is 0.29 μ m, and bubble occupied area rate is 16%; (d) bubble diameter is 0.34 μ m, and bubble occupied area rate is 22%; (e) bubble diameter is 0.42 μ m, and bubble occupied area rate is 32% (with reference to Figure 29).Like this, can obtain the inclination foam that the bubble distribution has continuous slope.

＜embodiment 7-4 〉

In the operation (1) of embodiment 7-1, carry out the lamination coating, make coating layer thickness reach 400 μ m.To this laminate with 1000mJ/cm ²Carry out irradiation ultraviolet radiation.What ultraviolet lamp used is the metal halide lamp that is output as 120w/cm.Postradiation laminate is passed through between two different metal rollers of temperature, implemented heat treated, thereby foam.At this moment, the temperature of a metal roller is adjusted into 100 ℃, the temperature of another metal roller is adjusted into 130 ℃.

Consequently can obtain to have the inclined foam of following slope: from the surface of the laminate that contacts with the high cylinder of temperature to another surface (surface of the laminate that contacts with the low cylinder of temperature), bubble diameter is 0.1～1 μ m, and bubble occupied area rate is 4～30%.

＜embodiment 7-5 〉

The three kind decomposability compounds of the copolymerization ratio of using tert-butyl acrylate and methacrylic ester under for example: tert-butyl acrylate/methacrylic ester=80/20,60/40,40/60, make the sheet that forms according to the said sequence lamination by coating.At this moment, relative 100 parts of decomposability compounds in each layer mix 3 parts of BBI-109.It is thick that the thickness of each layer is adjusted into 50 μ m.To this laminate with 1000mJ/cm ²Irradiation ultraviolet radiation.What ultraviolet lamp used is the metal halide lamp that is output as 120w/cm.After irradiation,, make its foaming with 110 ℃ of heating 2 minutes.

Consequently, can obtain bubble diameter and bubble occupied area rate increases and bubble is distributed in thickness direction and is the inclined foam that changes interimly from the high layer of the low course of the copolymerization ratio of tert-butyl acrylate.

＜embodiment 8-1 〉

The making of thin light guide panel

(1) sheet of foaminess composition

Relatively as 00 part of the copolymer 1 of tert-butyl acrylate (60 weight %), methacrylic tert-butyl acrylate (40 weight %) and the methacrylic acid (10 weight %) of decomposability compound, mixing is as two (4-tert-butyl-phenyl) salt compounded of iodine (trade marks: BBI-109 of perfluorinated butane sulfonic acid of salt compounded of iodine series acid producing agent, the manufacturing of ミ De リ chemistry) 3 part, with this mixture dissolving, be modulated into ethyl acetate solution (solids component amount: 25%).Use the paint daubs (trade mark: De Network one ズ レ one De TD type of coating thickness 300 μ m, YOSHIMITSUSEIKI makes) at silicon PET sheet (trade mark: Le ミ ラ-SP-PET-01-75BU, the manufacturing of パ Na Star Network) is coated with after the above-mentioned mixing solutions on the silicon treat surface, in temperature is 110 ℃ freeze-day with constant temperature machine, solvent evaporation is removed, obtain water white coating layer.This coating layer is peeled off from silicon PET sheet, is the spumescence film of 50 μ m thereby obtain thickness.

(2) plate forming

The foaminess film of making in the described operation (1) is cut into the size of long 50mm, wide 35mm, and with its overlapping 12, shown in Figure 49 (a) and (b), be clamped in the concora crush mould (size: long 50mm, wide 35mm) of surface smoothing, (trade mark: TOYOSEIKI makes to use manual squeezing machine, Mini TEST PRESS-10) carries out hot-pressing (squeeze pressure: 6MPa, pressing temperature: 150 ℃, 3 minutes).Then, as shown in figure 49, return to normal pressure, when air cooling to 40 ℃, mould is taken off, obtain water white foaminess flat board.

(3) uviolizing

As shown in figure 49, the photomask (size: long 50mm, wide 35mm) of silica glass system is covered on whole upper surfaces of the foaminess flat board that obtains by described operation (2), and the side carries out uviolizing from it.Photomask uses is that its transmitance is a continually varying tilt mode on the length direction of 0～40% (the mensuration wavelength is 254nm).Ultraviolet ray uses metal halide lamp (trade mark: ultraviolet curing is made with many metalized lamps M03-L31, ア イ グ ラ Off イ Star Network (strain)) as light source, with 2200mJ/cm ²The irradiation light amount shine.After irradiation, take off photomask, obtain the water white foaminess flat board identical with operation (1).

(4) foamable

Shown in Figure 49 (e), identical with described operation (2), will be clamped in the concora crush mould by the foaminess flat board behind the irradiation ultraviolet radiation of described operation (3) acquisition, with manual squeezing machine hot-pressing, foam simultaneously (squeeze pressure: 4MPa, pressing temperature: 130 ℃, 2 minutes).Then, shown in Figure 49 (f), under the state that keeps pressurization, water coolant is circulated at mould inside, be cooled fast to 50 ℃.Then, shown in Figure 49 (g), return to normal pressure, and with air cooling to 40 ℃, mold removal shown in Figure 49 (h), obtains the light guiding section that is formed by foams.

The light guiding section that is obtained be thickness from plane of incidence side (light source side when using) to its reverse direction face side (plane of incidence and opposition side) as surface illuminating device uniform tabular, and its thickness is 600 μ m.(trade mark: Mitutoyo makes, MCD-25M) to measure thickness use milscale.In addition, the transparency of this light guiding section is continually varying (transmissivity of photomask is up to the degree of translucentization).

(5) foam structure evaluation

Utilize sem observation to profile image calculate the bubble diameter (mean value of bubble diameter) of the light guiding section that obtains by described operation (4) and bubble occupied area rate (when the largest air bubbles diameter less than 1 μ m, at 100 μ m ²Section in, more than the largest air bubbles diameter is 1 μ m during to 5 μ m, at 2500 μ m ²Section in, when the largest air bubbles diameter is that 5 μ m are when above, at 10000 μ m ²Section in, the area ratio that the bubble section is shared).

The light guiding section that is immersed in the liquid nitrogen is carried out freezing cutting side by side from the plane of incidence to the opposing face, after this cut surface is carried out vapor deposition treatment, utilize scanning electron microscope (trade mark: S-510, the Hitachi makes, expansion multiplying power: 5000 times) observe under, thus the observation image of acquisition section.

And, carry out after 2 values handle will observing bubble in the image and matrix, use image analysis apparatus (trade mark: イ メ one ジ ア Na ラ イ ザ one V10 (image dissector V10), TOYOBO makes) to calculate bubble diameter and bubble occupied area rate.

In the light guiding section that is obtained, from the plane of incidence to the opposite face, bubble diameter and bubble occupied area rate are the tilt distribution that increases gradually.The largest air bubbles diameter is 0.3 μ m.In addition, bubble occupied area rate changes to 16% from 0%.

(6) surface illuminating device and luminous evaluation

On the side of the light guide that the light guiding section that obtains by described operation (4) forms, dispose four white chip LEDs (a day inferior chemistry is made physical dimension: long 1.2mm, wide 1.8mm, high 0.6mm) equably.It just in time is the direction of translucentization of light guiding section that the incident direction of this moment is adjusted into.In addition, to form the concavo-convex prismatic lens of triangular prism shape at a side (exit facet) configuration surface of light guiding section, on the face of its opposition side, dispose light-reflecting sheet (reflectivity is more than 90%), above-mentioned whole opticses are assembled in the white framework, thereby obtain surface illuminating device.

With the uniformly light-emitting of the surface illuminating device that visual valuation obtained, the result is that even do not make light diffusion sheet overlapping, also demonstration is luminous uniformly, can not observe the bubble distribution pattern.That is, though can easily obtain to be difficult in the prior art obtain, thin thickness do not use light diffusion sheet not have brightness disproportionation but the light guide of uniformly light-emitting to 0.6mm yet.

＜embodiment 8-2 〉

By with operation (1)～(3) operation much at one of embodiment 8-1, obtain foaminess flat board (A).But, use be the little photomask (size: long 48mm, wide 31mm) of photomask size that uses in the operation (3) than embodiment 8-1.And, with one side of the length direction of this photomask and one side central alignment of the length direction of foaminess flat board, make other three avris spaced slots cover the foaminess flat board (being 2mm on all directions), carry out uviolizing.

This foaminess flat board (A) and three foaminess films (B) are carried out overlapping, this foaminess film (B) is whole irradiation ultraviolet radiation (the irradiation light amount 2200mJ/cm by the foaminess film that obtains to the operation (1) by embodiment 8-1 ²) obtain, similarly carry out hot-pressing with the operation (4) of embodiment 8-1 again.Consequently, can obtain to have the one-piece type light guide of the photo-emission part that end face and lower surface at light guiding section foam to high-density.The light guiding section thickness of the light guide that is obtained equates with the light guiding section of embodiment 8-1.

The bubble diameter of the light guide that obtained and bubble occupied area rate and embodiment 8-1 are calculated in the same manner, and the result is, and is with regard to light guiding section, equal with embodiment 8-1.On the other hand, the bubble diameter of photo-emission part is 0.4 μ m, and generally speaking is uniform.In addition, the bubble occupied area rate of photo-emission part is 52%, and generally speaking is uniform.This photo-emission part is different with translucent light guiding section, has the high light reflectivity rate more than 90%.

Uniformly light-emitting is estimated with the operation (6) of embodiment 8-1 roughly the samely, but do not used the light-reflecting sheet that is configured on the bright dipping opposite face.This one-piece type light guide not only with embodiment 8-1 uniformly light-emitting in the same manner, and utilize the photo-emission part of end face, also avoided light taking place and leaked from the slit between the white framework.

＜embodiment 8-3 〉

In the mould that is arranged with the concaveconvex shape of triangular prism shape regularly (size: long 50mm * wide 35mm, dark 0.1mm), filling epoxy acrylic is that afterwards, irradiation ultraviolet radiation makes its curing to ultraviolet curing resin (Japanese synthetic rubber manufacturing).On its solidified surface, the foaminess flat board that overlapping operation by embodiment 8-1 (3) obtains carries out hot-pressing and makes its foaming.Consequently, can obtain to have the one-piece type light guide of prism portion at the upper surface of light guiding section.The thickness of the light guiding section of the light guide that is obtained equates with the light guiding section of embodiment 8-1.

When the bubble diameter of the light guide that obtained and bubble occupied area rate and embodiment 8-1 are similarly calculated, with regard to light guiding section, identical with embodiment 8-1.On the other hand, do not find foamy structure in the prism portion.

In the same manner uniformly light-emitting is estimated with the operation (6) of embodiment 8-1, but do not had to use the prismatic lens that is configured on the emergent light opposite face.This one-piece type light guide not only with embodiment 8-1 uniformly light-emitting similarly, even and do not use prismatic lens can obtain good surface illuminating device in addition yet.

＜embodiment 8-4 〉

In the mould that is arranged with the concaveconvex shape of triangular prism shape regularly (size: long 50mm * wide 35mm, dark 0.1mm), filling epoxy acrylic is that afterwards, irradiation ultraviolet radiation makes its curing to ultraviolet curing resin (Japanese synthetic rubber manufacturing).On its solidified surface, foaminess flat board (A) and foaminess film (B) with the overlapping embodiment 8-2 of this order carry out hot-pressing simultaneously.Consequently, can obtain to comprise the one-piece type light guide of light guiding section, photo-emission part and prism portion.The thickness of the light guiding section of the light guide that is obtained equates with the light guiding section of embodiment 8-1.

The bubble diameter of the light guide that obtained and bubble occupied area rate and embodiment 8-1 are similarly calculated, consequently, with regard to light guiding section and photo-emission part, identical with embodiment 8-2.On the other hand, do not find foamy structure in the prism portion.

In the same manner uniformly light-emitting is estimated with the operation (6) of embodiment 8-1, but do not used prismatic lens and light-reflecting sheet.Because do not have independently parts, so can omit the white framework that is used to take in.

This one-piece type light guide not only with embodiment 8-1 uniformly light-emitting similarly, even and do not use prismatic lens, light-reflecting sheet and white framework in addition, also can obtain good surface illuminating device.

＜embodiment 8-5 〉

Same with the operation (3) of embodiment 8-1, across the mask of tilt mode the foaminess film that an operation by embodiment 8-1 (1) obtains is carried out uviolizing.Then, with the operation (4) of embodiment 8-1 in the same manner, with polycarbonate resin plate (PC plate: thickness 550 μ m) carry out hot-pressing as transparent resin.The integral thickness of the light guiding section of the light guide that is obtained equates with the light guiding section of embodiment 8-1, is 600 μ m.But wherein, the thickness of the part that is formed by foams is 50 μ m.

The bubble diameter of the light guide that obtained and bubble occupied area rate and embodiment 8-1 are similarly calculated, and the result is, and is with regard to the part that is formed by foams, identical with embodiment 8-1.On the other hand, in resin board, do not find foamy structure.With regard to light guiding section generally speaking, bubble occupied area rate changes to 1.3% from 0%.

In addition, uniformly light-emitting is estimated with the operation (6) of embodiment 8-1, the result is to obtain the uniformly light-emitting identical with embodiment 8-1 roughly the samely.

＜embodiment 8-6 〉

Photomask across dot pattern carries out uviolizing (irradiation light amount 330mJ/cm to the foaminess film that an operation by embodiment 8-1 (1) obtains ²).At this moment, use is the pattern that spot diameter and density increase gradually.Then, such according to the operation (4) of embodiment 8-1, carry out hot-pressing with polycarbonate resin plate (thickness 550 μ m) as transparent resin.The integral thickness of the light guiding section of the light guide that is obtained is identical with the light guiding section of embodiment 8-1, is 600 μ m.But wherein, the thickness of the part that is formed by foams is 50 μ m.

Carry out similarly the bubble diameter and the bubble occupied area rate of the light guide that obtained are calculated with embodiment 8-1, the result is with regard to the part that is formed by foams, to form the tilt distribution that point-like portion increases gradually from the plane of incidence to the opposite face.Largest air bubbles diameter in the point-like portion is 0.1 μ m, and bubble occupied area rate is 4.5% and is roughly uniform in point.On the other hand, in resin board, do not find foamy structure.With regard to light guiding section generally speaking, bubble occupied area rate changes to 0.38% from 0%.

In addition, uniformly light-emitting is estimated with the operation (6) of embodiment 8-1, the result is roughly the samely, even not overlapping light diffusion sheet, also demonstration is luminous uniformly, can not observe the pattern of point-like portion.That is, though can easily obtain to be difficult in the prior art obtain, thin thickness do not use light diffusion sheet not have brightness disproportionation but the light guide of uniformly light-emitting to 0.6mm yet.

In addition, in the light guide of present embodiment, incident light reflects according to the different point-like thing of specific refractory power, penetrates light according to the Snell the law of refraction.

The result of above embodiment 8-1～8-6 is summarized in the table 3.

Table 3

Utilizability on the industry

Utilize the present invention, below bubble diameter is 10 μ m even be in the foams of the micro air bubble below the 1 μ m, can easily, stably realize having foaming structure control and the shape control of micro air bubble foams of thickness, shape and the foaming structure of expectation. In addition, utilize the high functionality micro air bubble foams that do not have in the thus obtained prior art, not only have the low effect of control mechanics intensity, alleviate contraction and the effect of warpage and the effect that improves dimensional stability of the processing and forming product of injection moulding etc., and can easily produce the raw material of light specular scattering characteristic, dielectric characteristic and the insulating characteristics etc. that can freely control foams. Play very large effect in various fields such as packaging material or construction material, medical material, electrical equipment material, electronic information material, automotive materials. In addition, can provide a kind of bubble distribution of in above-mentioned various uses, following also to produce the high functionality foams that foam characteristics distributes. And, can make by simple manufacturing process the light conductor of liquid crystal indicator etc.

Claims (9)

1. the manufacture method of foams comprises following operation:

Irradiation process, to foaminess composition irradiation active energy ray, the alkali that described foaminess composition contains the acidic acid producing agent of the effect that utilizes active energy ray or produces alkali produces agent, also contains to have the compound that decomposes the reducing foaming property functional group that discharges more than one lower boiling volatile matter with acid or alkali reaction; And

Foamed process in decomposition discharges the temperature province of described lower boiling volatile matter, makes the foaming of foaminess composition under pressure-controlling.

2. the manufacture method of foams according to claim 1 is characterized in that,

Comprise forming process, in foamed process or before arbitrary the time photoetching form foaminess composition.

3. the manufacture method of foams according to claim 2 is characterized in that, has forming process before irradiation process.

4. the manufacture method of foams according to claim 2 is characterized in that, has forming process between irradiation process and foamed process.

5. the manufacture method of foams according to claim 2 is characterized in that, foamed process and forming process are carried out simultaneously.

6. the manufacture method of foams is characterized in that,

Has foamed process, in described foamed process, produce agent, also contain foaminess composition and discharge the temperature province internal radiation active energy ray of described lower boiling volatile matter to the alkali that contains the acidic acid producing agent of the effect that utilizes active energy ray or produce alkali, under pressure-controlling, make the foaming of foaminess composition simultaneously in decomposition with the compound that decomposes the reducing foaming property functional group that discharges more than one lower boiling volatile matter with acid or alkali reaction.

7. according to the manufacture method of each described foams in the claim 1 to 6, it is characterized in that, while after foamed process, have the pressure-controlling of carrying out refrigerative operation.

8. the manufacture method of inhomogeneous foams is characterized in that, in the manufacture method of the described foams of claim 3, and any uneven distribution of being scheduled to that forms more than in the and the following:

(a) the radioactive rays energy that the molding that is shaped by the preliminary forming operation is applied;

(b) heat energy that molding is applied by the foams forming process;

(c) the reducing foaming property functional group concentration in the molding;

(d) acid producing agent in the molding or alkali produce the concentration of agent.

9. use the light guide of the described inhomogeneous foams of claim 8.

Images